Fatty amines, amidoamines, and their derivatives from natural oil metathesis

ABSTRACT

Fatty amine compositions made from a metathesis-derived C10-C17 monounsaturated acid, octadecene-1,18-dioic acid, or their ester derivatives are disclosed. In another aspect, fatty amidoamines made by reacting a metathesis-derived C10-C17 monounsaturated acid, octadecene-1,18-dioic acid, or their ester derivatives with an aminoalkyl-substituted tertiary amine are disclosed. The fatty amines or amidoamines are advantageously sulfonated, sulfitated, oxidized, or reduced. In other aspects, the ester derivative is a modified triglyceride made by self-metathesis of a natural oil or an unsaturated triglyceride made by cross-metathesis of a natural oil with an olefin.

This applcation is a division of U.S. patent application Ser. No.13/878,981, filed May 15, 2013, now allowed, which is a national stagefiling under 35 U.S.C §317 of PCT/US2011/057602, filed Oct. 25, 2011,which claims the benefit of U.S. provisional applcations 61/406,570,61/406,556, and 61/406,547, all filed Oct. 25, 2010.

FIELD OF THE INVENTION

The invention relates to fatty amines, amidoamines, and derivativecompositions that originate from natural resources, particularly naturaloils and their metathesis products.

BACKGROUND OF THE INVENTION

“Fatty amines” generally have a nonpolar chain of six or more carbons,typically 6-30 carbons, and at least one polar end group comprising orderived from an amine, for example, a tertiary amine. Fatty amines havevalue in and of themselves, or they can be modified to provide differentutility. For instance, oxidation of a tertiary amine group provides anamine oxide with properties unlike the free amine. A variety ofquaternization methods further expand the utility of fatty tertiaryamines as intermediate targets.

Fatty amines and/or their derivatives have been used in a wide range ofend-use applications, including fabric softening or other antistaticuses (see U.S. Pat. Nos. 3,468,869; 3,943,234; and 6,110,886), shampoosand hair conditioning (U.S. Pat. Nos. 4,714,610 and 5,167,864), cleanersand detergents including hard surface cleaners (U.S. Pat. No. 5,858,955and U.S. Pat. Appl. Publ. Nos. 2010/0184855 and 2009/0305938), corrosioninhibitors (U.S. Pat. No. 5,322,630), and agricultural surfactants (U.S.Pat. Nos. 5,226,943 and 5,668,085).

Fatty tertiary amines can be made by converting fatty esters or acidswith a secondary amine to the amide derivative, followed by reduction ofthe carbonyl to give a terminal tertiary amine. In a preferred approach,the reduction step is avoided by reacting a fatty ester with anaminoalkyl-substituted tertiary amine. For instance,N,N-dimethyl-1,3-propanediamine (DMAPA) reacts with a fatty methylester, triglyceride or fatty acid to give a fatty amidoamine. Theamidoamine has a terminal tertiary amine group that is well suited tofurther functionalization by oxidation or quaternization.

Fatty amines can also be made by direct amination of fatty alcohols,usually with a copper and/or nickel-based catalyst (see, e.g., U.S. Pat.Nos. 3,497,555; 4,594,455; and 4,994,622), or in multiple steps from thefatty alcohol by first converting the alcohol to a halide, sulfonateester, or the like, and then reacting with ammonia or a primary orsecondary amine.

The fatty acids or esters used to make fatty amines and theirderivatives are usually made by hydrolysis or transesterification oftriglycerides, which are typically animal or vegetable fats.Consequently, the fatty portion of the acid or ester will typically have6-22 carbons with a mixture of saturated and internally unsaturatedchains. Depending on source, the fatty acid or ester often has apreponderance of C₁₆ to C₂₂ component. For instance, methanolysis ofsoybean oil provides the saturated methyl esters of palmitic (C₁₆) andstearic (C₁₈) acids and the unsaturated methyl esters of oleic (C₁₈mono-unsaturated), linoleic (C₁₈ di-unsaturated), and α-linolenic (C₁₈tri-unsaturated) acids. The unsaturation in these acids has eitherexclusively or predominantly cis-configuration.

Recent improvements in metathesis catalysts (see J. C. Mol, Green Chem.4 (2002) 5) provide an opportunity to generate reduced chain length,monounsaturated feedstocks, which are valuable for making detergents andsurfactants, from C₁₆ to C₂₂-rich natural oils such as soybean oil orpalm oil. Soybean oil and palm oil can be more economical than, forexample, coconut oil, which is a traditional starting material formaking detergents. As Professor Mol explains, metathesis relies onconversion of olefins into new products by rupture and reformation ofcarbon-carbon double bonds mediated by transition metal carbenecomplexes. Self-metathesis of an unsaturated fatty ester can provide anequilibrium mixture of starting material, an internally unsaturatedhydrocarbon, and an unsaturated diester. For instance, methyl oleate(methyl cis-9-octadecenoate) is partially converted to 9-octadecene anddimethyl 9-octadecene-1,18-dioate, with both products consistingpredominantly of the trans-isomer. Metathesis effectively isomerizes thecis-double bond of methyl oleate to give an equilibrium mixture of cis-and trans-isomers in both the “unconverted” starting material and themetathesis products, with the trans-isomers predominating.

Cross-metathesis of unsaturated fatty esters with olefins generates newolefins and new unsaturated esters that can have reduced chain lengthand that may be difficult to make otherwise. For instance,cross-metathesis of methyl oleate and 3-hexene provides 3-dodecene andmethyl 9-dodecenoate (see also U.S. Pat. No. 4,545,941). Terminalolefins are particularly desirable synthetic targets, and ElevanceRenewable Sciences, Inc. recently described an improved way to preparethem by cross-metathesis of an internal olefin and an α-olefin in thepresence of a ruthenium alkylidene catalyst (see U.S. Pat. Appl. Publ.No. 2010/0145086). A variety of cross-metathesis reactions involving anα-olefin and an unsaturated fatty ester (as the internal olefin source)are described. Thus, for example, reaction of soybean oil with propylenefollowed by hydrolysis gives, among other things, 1-decene, 2-undecenes,9-decenoic acid, and 9-undecenoic acid. Despite the availability (fromcross-metathesis of natural oils and olefins) of unsaturated fattyesters having reduced chain length and/or predominantlytrans-configuration of the unsaturation, fatty amines and theirderivatives made from these feedstocks appear to be unknown. Moreover,fatty amines and their derivatives have not been made from the C₁₈unsaturated diesters that can be made readily by self-metathesis of anatural oil.

In sum, traditional sources of fatty acids and esters used for makingfatty amines and their derivatives generally have predominantly (orexclusively) cis-isomers and lack relatively short-chain (e.g., C₁₀ orC₁₂) unsaturated fatty portions. Metathesis chemistry provides anopportunity to generate precursors having shorter chains and mostlytrans-isomers, which could impart improved performance when theprecursors are converted to downstream compositions (e.g., insurfactants). New C₁₈ difunctional fatty amines and derivatives are alsopotentially available from oil or C₁₀ unsaturated acid or esterself-metathesis. In addition to an expanded variety of precursors, theunsaturation present in the precursors allows for furtherfunctionalization, e.g., by sulfonation or sulfitation.

SUMMARY OF THE INVENTION

In one aspect, the invention relates to fatty amine compositions. Thefatty amines are made from a metathesis-derived C₁₀-C₁₇, monounsaturatedacid, octadecene-1,18-dioic acid, or their ester derivatives. The fattyamines can be made in several ways. In one synthetic approach, themetathesis-derived acid or ester is reacted with ammonia or a primary orsecondary amine, and the resulting fatty amide is reduced to give thefatty amine. In another approach, the metathesis-derived acid or esteris reduced to give a fatty alcohol, and the fatty alcohol is aminated ina single or multiple steps.

In another aspect, the invention relates to fatty amidoamines made byreacting a metathesis-derived C₁₀-C₁₇ monounsaturated acid,octadecene-1,18-dioic acid, or their ester derivatives with anaminoalkyl-substituted tertiary amine such as DMAPA.

The invention includes derivatives made by sulfonating, sulfitating, oroxidizing the fatty amines or amidoamines.

In one aspect, the ester derivative of the C₁₀-C₁₇ monounsaturated acidor octadecene-1,18-dioic acid is a lower alkyl ester. In other aspects,the ester derivative is a modified triglyceride made by self-metathesisof a natural oil or an unsaturated triglyceride made by cross-metathesisof a natural oil with an olefin.

Fatty amines and amidoamines and their derivatives are valuable for awide variety of end uses, including cleaners, fabric treatment, hairconditioning, personal care (liquid cleansing products, conditioningbars, oral care products), antimicrobial compositions, agriculturaluses, and oil field applications.

DETAILED DESCRIPTION OF THE INVENTION

In one aspect, the invention relates to fatty amines made from ametathesis-derived C₁₀-C₁₇ monounsaturated acid, octadecene-1,18-dioicacid, or their ester derivatives.

The C₁₀-C₁₇ monounsaturated acid, octadecene-1,18-dioic acid, or theirester derivatives used as a reactant is derived from metathesis of anatural oil. Traditionally, these materials, particularly theshort-chain acids and derivatives (e.g., 9-decylenic acid or9-dodecylenic acid) have been difficult to obtain except in lab-scalequantities at considerable expense. However, because of the recentimprovements in metathesis catalysts, these acids and their esterderivatives are now available in bulk at reasonable cost. Thus, theC₁₀-C₁₇ monounsaturated acids and esters are conveniently generated bycross-metathesis of natural oils with olefins, preferably α-olefins, andparticularly ethylene, propylene, 1-butene, 1-hexene, 1-octene, and thelike. Self-metathesis of the natural oil or a C₁₀ acid or esterprecursor (e.g., methyl 9-decenoate) provides the C₁₈ diacid or diesterin optimal yield when it is the desired product.

Preferably, at least a portion of the C₁₀-C₁₇ monounsaturated acid has“Δ⁹” unsaturation, i.e., the carbon-carbon double bond in the C₁₀-C₁₇acid is at the 9-position with respect to the acid carbonyl. In otherwords, there are preferably seven carbons between the acid carbonylgroup and the olefin group at C9 and C10. For the C₁₁ to C₁₇ acids, analkyl chain of 1 to 7 carbons, respectively is attached to C10.Preferably, the unsaturation is at least 1 mole % trans-Δ⁹, morepreferably at least 25 mole % trans-Δ⁹, more preferably at least 50 mole% trans-Δ⁹, and even more preferably at least 80% trans-Δ⁹. Theunsaturation may be greater than 90 mole %, greater than 95 mole %, oreven 100% trans-Δ⁹. In contrast, naturally sourced fatty acids that haveΔ⁹ unsaturation, e.g., oleic acid, usually have ˜100% cis-isomers.

Although a high proportion of trans-geometry (particularly trans-Δ⁹geometry) may be desirable in the metathesis-derived fatty amines andderivatives of the invention, the skilled person will recognize that theconfiguration and the exact location of the carbon-carbon double bondwill depend on reaction conditions, catalyst selection, and otherfactors. Metathesis reactions are commonly accompanied by isomerization,which may or may not be desirable. See, for example, G. Djigoué and M.Meier, Appl. Catal. A: General 346 (2009) 158, especially FIG. 3. Thus,the skilled person might modify the reaction conditions to control thedegree of isomerization or alter the proportion of cis- andtrans-isomers generated. For instance, heating a metathesis product inthe presence of an inactivated metathesis catalyst might allow theskilled person to induce double bond migration to give a lowerproportion of product having trans-Δ⁹ geometry.

An elevated proportion of trans-isomer content (relative to the usualall-cis configuration of the natural monounsaturated acid or ester)imparts different physical properties to fatty amine compositions madefrom them, including, for example, modified physical form, meltingrange, compactability, and other important properties. These differencesshould allow formulators that use fatty amines and their amine oxidederivatives greater latitude or expanded choice as they use the fattyamines or derivatives in cleaners, fabric treatment, personal care,agricultural uses, and other end uses.

Suitable metathesis-derived C₁₀-C₁₇ monounsaturated acids include, forexample, 9-decylenic acid (9-decenoic acid), 9-undecenoic acid,9-dodecylenic acid (9-dodecenoic acid), 9-tridecenoic acid,9-tetradecenoic acid, 9-pentadecenoic acid, 9-hexadecenoic acid,9-heptadecenoic acid, and the like, and their ester derivatives.

Usually, cross-metathesis or self-metathesis of the natural oil isfollowed by separation of an olefin stream from a modified oil stream,typically by distilling out the more volatile olefins. The modified oilstream is then reacted with a lower alcohol, typically methanol, to giveglycerin and a mixture of alkyl esters. This mixture normally includessaturated C₆-C₂₂ alkyl esters, predominantly C₁₆-C₁₈ alkyl esters, whichare essentially spectators in the metathesis reaction. The rest of theproduct mixture depends on whether cross- or self-metathesis is used.When the natural oil is self-metathesized and then transesterified, thealkyl ester mixture will include a C₁₈ unsaturated diester. When thenatural oil is cross-metathesized with an α-olefin and the productmixture is transesterified, the resulting alkyl ester mixture includes aC₁₀ unsaturated alkyl ester and one or more C₁₁ to C₁₇ unsaturated alkylester coproducts in addition to the glycerin by-product. The terminallyunsaturated C₁₀ product is accompanied by different coproducts dependingupon which α-olefin(s) is used as the cross-metathesis reactant. Thus,1-butene gives a C₁₂ unsaturated alkyl ester, 1-hexene gives a C₁₄unsaturated alkyl ester, and so on. As is demonstrated in the examplesbelow, the C₁₀ unsaturated alkyl ester is readily separated from the C₁₁to C₁₇ unsaturated alkyl ester and each is easily purified by fractionaldistillation. These alkyl esters are excellent starting materials formaking the inventive fatty amine compositions.

Natural oils suitable for use as a feedstock to generate the C₁₀-C₁₇monounsaturated acid, octadecene-1,18-dioic acid, or their esterderivatives from self-metathesis or cross-metathesis with olefins arewell known. Suitable natural oils include vegetable oils, algal oils,animal fats, tall oils, derivatives of the oils, and combinationsthereof. Thus, suitable natural oils include, for example, soybean oil,palm oil, rapeseed oil, coconut oil, palm kernel oil, sunflower oil,safflower oil, sesame oil, corn oil, olive oil, peanut oil, cottonseedoil, canola oil, castor oil, tallow, lard, poultry fat, fish oil, andthe like. Soybean oil, palm oil, rapeseed oil, and mixtures thereof arepreferred natural oils.

Genetically modified oils, e.g., high-oleate soybean oil or geneticallymodified algal oil, can also be used. Preferred natural oils havesubstantial unsaturation, as this provides a reaction site for themetathesis process for generating olefins. Particularly preferred arenatural oils that have a high content of unsaturated fatty groupsderived from oleic acid. Thus, particularly preferred natural oilsinclude soybean oil, palm oil, algal oil, and rapeseed oil.

A modified natural oil, such as a partially hydrogenated vegetable oil,can be used instead of or in combination with the natural oil. When anatural oil is partially hydrogenated, the site of unsaturation canmigrate to a variety of positions on the hydrocarbon backbone of thefatty ester moiety. Because of this tendency, when the modified naturaloil is self-metathesized or is cross-metathesized with the olefin, thereaction products will have a different and generally broaderdistribution compared with the product mixture generated from anunmodified natural oil. However, the products generated from themodified natural oil are similarly converted to inventive fatty amine oramidoamine compositions.

An alternative to using a natural oil as a feedstock to generate theC₁₀-C₁₇ monounsaturated acid, octadecene-1,18-dioic acid, or their esterderivatives from self-metathesis or cross-metathesis with olefins is amonounsaturated fatty acid obtained by the hydrolysis of a vegetable oilor animal fat, or an ester or salt of such an acid obtained byesterification of a fatty acid or carboxylate salt, or bytransesterification of a natural oil with an alcohol. Also useful asstarting compositions are polyunsaturated fatty esters, acids, andcarboxylate salts. The salts can include an alkali metal (e.g., Li, Na,or K); an alkaline earth metal (e.g., Mg or Ca); a Group 13-15 metal(e.g., B, Al, Sn, Pb, or Sb), or a transition, lanthanide, or actinidemetal. Additional suitable starting compositions are described at pp.7-17 of PCT application WO 2008/048522, the contents of which areincorporated by reference herein.

The other reactant in the cross-metathesis reaction is an olefin.Suitable olefins are internal or α-olefins having one or morecarbon-carbon double bonds. Mixtures of olefins can be used. Preferably,the olefin is a monounsaturated C₂-C₁₀ α-olefin, more preferably amonounsaturated C₂-C₈ α-olefin. Preferred olefins also include C₄-C₉internal olefins. Thus, suitable olefins for use include, for example,ethylene, propylene, 1-butene, cis- and trans-2-butene, 1-pentene,isohexylene, 1-hexene, 3-hexene, 1-heptene, 1-octene, 1-nonene,1-decene, and the like, and mixtures thereof.

Cross-metathesis is accomplished by reacting the natural oil and theolefin in the presence of a homogeneous or heterogeneous metathesiscatalyst. The olefin is omitted when the natural oil isself-metathesized, but the same catalyst types are generally used.Suitable homogeneous metathesis catalysts include combinations of atransition metal halide or oxo-halide (e.g., WOCl₄ or WCl₆) with analkylating cocatalyst (e.g., Me₄Sn). Preferred homogeneous catalysts arewell-defined alkylidene (or carbene) complexes of transition metals,particularly Ru, Mo, or W. These include first and second-generationGrubbs catalysts, Grubbs-Hoveyda catalysts, and the like. Suitablealkylidene catalysts have the general structure:M[X¹X²L¹L²(L³)_(n)]=C_(m)=C(R¹)R²where M is a Group 8 transition metal, L¹, L², and L³ are neutralelectron donor ligands, n is 0 (such that L³ may not be present) or 1, mis 0, 1, or 2, X¹ and X² are anionic ligands, and R¹ and R² areindependently selected from H, hydrocarbyl, substituted hydrocarbyl,heteroatom-containing hydrocarbyl, substituted heteroatom-containinghydrocarbyl, and functional groups. Any two or more of X¹, X², L¹, L²,L³, R¹ and R² can form a cyclic group and any one of those groups can beattached to a support.

First-generation Grubbs catalysts fall into this category where m=n=0and particular selections are made for n, X¹, X², L¹, L², L³, R¹ and R²as described in U.S. Pat. Appl. Publ. No. 2010/0145086 (“the '086publication”), the teachings of which related to all metathesiscatalysts are incorporated herein by reference.

Second-generation Grubbs catalysts also have the general formuladescribed above, but L¹ is a carbene ligand where the carbene carbon isflanked by N, O, S, or P atoms, preferably by two N atoms. Usually, thecarbene ligand is party of a cyclic group. Examples of suitablesecond-generation Grubbs catalysts also appear in the '086 publication.

In another class of suitable alkylidene catalysts, L¹ is a stronglycoordinating neutral electron donor as in first- and second-generationGrubbs catalysts, and L² and L³ are weakly coordinating neutral electrondonor ligands in the form of optionally substituted heterocyclic groups.Thus, L² and L³ are pyridine, pyrimidine, pyrrole, quinoline, thiophene,or the like.

In yet another class of suitable alkylidene catalysts, a pair ofsubstituents is used to form a bi- or tridentate ligand, such as abiphosphine, dialkoxide, or alkyldiketonate. Grubbs-Hoveyda catalystsare a subset of this type of catalyst in which L² and R² are linked.Typically, a neutral oxygen or nitrogen coordinates to the metal whilealso being bonded to a carbon that is α-, β-, or γ-with respect to thecarbene carbon to provide the bidentate ligand. Examples of suitableGrubbs-Hoveyda catalysts appear in the '086 publication.

The structures below provide just a few illustrations of suitablecatalysts that may be used:

Heterogeneous catalysts suitable for use in the self- orcross-metathesis reaction include certain rhenium and molybdenumcompounds as described, e.g., by J. C. Mol in Green Chem. 4 (2002) 5 atpp. 11-12. Particular examples are catalyst systems that include Re₂O₇on alumina promoted by an alkylating cocatalyst such as a tetraalkyl tinlead, germanium, or silicon compound. Others include MoCl₃ or MoCl₅ onsilica activated by tetraalkyltins.

For additional examples of suitable catalysts for self- orcross-metathesis, see U.S. Pat. No. 4,545,941, the teachings of whichare incorporated herein by reference, and references cited therein.

Fatty amines of the invention can be made by reacting ametathesis-derived C₁₀-C₁₇ monounsaturated acid, octadecene-1,18-dioicacid, or their ester derivatives with ammonia or a primary or secondaryamine, followed by reduction of the resulting fatty amide. They can alsobe made reducing a metathesis-derived acid or ester derivative to afatty alcohol, followed by amination of the fatty alcohol. Thus,intermediates to the inventive fatty amines are metathesis-derived fattyalcohols or fatty amides.

In one aspect, the ester derivative is a lower alkyl ester, especially amethyl ester. The lower alkyl esters are preferably generated bytransesterifying a metathesis-derived triglyceride. For example,cross-metathesis of a natural oil with an olefin, followed by removal ofunsaturated hydrocarbon metathesis products by stripping, and thentransesterification of the modified oil component with a lower alkanolunder basic conditions provides a mixture of unsaturated lower alkylesters. The unsaturated lower alkyl ester mixture can be used “as is” tomake the intermediates for the inventive fatty amines or it can bepurified to isolate particular alkyl esters prior to making theintermediates.

In another aspect, the ester derivative is the metathesis-derivedtriglyceride discussed in the preceding paragraph. Instead oftransesterifying the metathesis-derived triglyceride with a loweralkanol to generate lower alkyl esters as described above, themetathesis-derived triglyceride, following olefin stripping, is reacteddirectly with ammonia or a primary or secondary amine to make a fattyamide mixture, which is then reduced to give the inventive fatty aminemixture. Alternatively, the metathesis-derived triglyceride, followingolefin stripping, is reduced to give a fatty alcohol mixture, which isthen aminated to give the inventive fatty amine mixture.

The skilled person will appreciate that “ester derivative” hereencompasses other acyl equivalents, such as acid chlorides, acidanhydrides, or the like, in addition to the lower alkyl esters andglyceryl esters discussed above.

In one synthetic approach, the metathesis-derived acid or esterderivative is reacted with ammonia or a primary or secondary amine togive a fatty amide, followed by reduction of the fatty amide to give thefatty amine.

Secondary amines are preferred reactants. Suitable secondary amines havea hydrogen and two hydrocarbyl groups attached to nitrogen. Thehydrocarbyl groups are preferably saturated or unsaturated linear,branched, or cyclic C₁-C₂₀ alkyl, C₆-C₂₀ aryl, or C₇-C₂₀ arylalkyl. Morepreferably, both of the hydrocarbyl groups are C₁-C₆ alkyl groups.Suitable secondary amines include, for example, N,N-dimethylamine,N,N-diethylamine, N,N,-dipropylamine, N,N-diisopropylamine,N,N-dibutylamine, N-methyl-N-cyclohexylamine, N-methyl-N-phenylamine,N-methyl-N-benzylamine, or the like, and mixtures thereof.N,N-Dimethylamine is cost-effective and is particularly preferred.

Suitable amines include etheramines. Thus, amines that are reactionproducts of ammonia or primary amines and an alkylene oxide, for example0.1 to 20 molar equivalents of ethylene oxide, propylene oxide, or thelike, can be used. The amine can be, for instance, a monoalkylatedderivative of a Jeffamine® M series polyether amine (product ofHuntsman). In some instances of using an etheramine, it may be necessaryto mask any hydroxyl functionality as an appropriate derivative, eitherbefore or after formation of the amide, so as to enable the subsequentreduction of this amide.

Although the fatty amides are made using a well-known process, theproduct mixture is unique because of the unconventional starting mixtureof acid or ester derivatives. The reactants are typically heated, withor without a catalyst under conditions effective to convert the startingacid, ester, or other derivative to an amide. The reaction temperatureis typically within the range of 40° C. to 300° C., preferably from 50°C. to 250° C., and more preferably from 50° C. to 200° C.

Reduction of the fatty amide to give a terminal amine is accomplishedusing well-known methods, including reactions with a hydride reducingagent (boranes, aluminum hydrides, borohydrides, or the like), orcatalytic hydrogenation. Suitable reducing reagents include, forexample, borane, borane dimethylsulfide, sodium borohydride/iodine,lithium cyanoborohydride, aluminum hydride, lithium aluminum hydride,diisobutylaluminum hydride, and the like. For additional examples, seeR. Larock, Comprehensive Organic Transformations: A Guide to FunctionalGroup Preparations (1989), pp. 432-434, and M. Smith and J. MarchMarch's Advanced Organic Chemistry, 5^(th) ed. (2001), pp. 1549-1550.

In an alternative synthetic approach, the fatty amine is made by firstreducing the metathesis-derived acid or ester derivative to give a fattyalcohol, followed by amination of the fatty alcohol. Themetathesis-derived acid or ester derivative is reduced to a fattyalcohol using a metal hydride reagent (sodium borohydride, lithiumaluminum hydride, or the like), catalytic hydrogenation, or otherwell-known techniques for generating the fatty alcohol (see, e.g., U.S.Pat. Nos. 2,865,968; 3,193,586; 5,124,491; 6,683,224; and 7,208,643, theteachings of which are incorporated herein by reference). Amination isthen preferably performed in a single step by reacting the fatty alcoholwith ammonia or a primary or secondary amine in the presence of anamination catalyst. Suitable amination catalysts are well known.Catalysts comprising copper, nickel, and/or alkaline earth metalcompounds are common. For suitable catalysts and processes foramination, see U.S. Pat. Nos. 5,696,294; 4,994,622; 4,594,455;4,409,399; and 3,497,555, the teachings of which are incorporated hereinby reference.

In a preferred aspect of the invention, the fatty amine is a fattyamidoamine made by reacting a metathesis-derived C₁₀-C₁₇ monounsaturatedacid, octadecene-1,18-dioic acid, or their ester derivatives with anaminoalkyl-substituted tertiary amine. This provides a product havingtertiary amine functionality without the need to reduce a fatty amide toa fatty amine with a strong reducing agent. Suitableaminoalkyl-substituted tertiary amines have a primary amino group at oneterminus, an alkylene group, and a tertiary amine group at the other endof the molecule. The alkylene group is preferably a C₂-C₆ linear orbranched diradical such as ethylene, propylene, butylene, or the like.Thus, suitable aminoalkyl-substituted tertiary amines include, forexample, N,N-dimethyl-1,2-ethanediamine, N,N-dimethyl-1,3-propanediamine(DMAPA), N,N-diethyl-1,3-propanediamine, N,N-dimethyl-1,4-butanediamine,and the like. DMAPA is particularly preferred. The primary amine groupexhibits good reactivity with the acid or ester derivative, while theterminal tertiary amine is preserved in the product and provides a sitefor further modification or functionalization. The obtained tertiaryamine is readily transformed, for example, into an amine oxide, betaine,sulfobetaine, or quaternary ammonium group.

The relative amounts of amine, ammonia, or aminoalkyl-substitutedtertiary amine that is reacted with the ester or acid reactants dependson the desired stoichiometry and is left to the skilled person'sdiscretion. In general, enough of the amine (or aminoalkyl-substitutedtertiary amine) is used to react with most or all of the available acidor ester groups, i.e., preferably greater than 90%, and more preferablygreater than 95%, of the available acid or ester groups.

Some fatty amines have the formula:R²(R³)NR¹

where:

-   R¹ is —C₁₀H₁₈—R⁴ or —C₁₈H₃₄—NR²R³; each of R² and R³ is    independently hydrogen, substituted or unsubstituted alkyl, aryl,    alkenyl, oxyalkylene, or polyoxyalkylene; and R⁴ is hydrogen or    C₁-C₇ alkyl. Preferably, R¹ is —(CH₂)₈—CH═CHR⁴ or    —(CH₂)₈—CH═CH—(CH₂)₈—NR²R³.

Some fatty amidoamines have the formula:R³(R²)N(CH₂)_(n)NH(CO)R¹

where:

-   R¹ is —C₉H₁₆—R⁴ or —C₁₆H₃₀—(CO)NH(CH₂)_(n)N(R²)R³; each of R² and R³    is independently substituted or unsubstituted alkyl, aryl, alkenyl,    oxyalkylene, or polyoxyalkylene; R⁴ is hydrogen or C₁-C₇ alkyl; and    n=2-8. Preferably, R¹ is —(CH₂)₇—CH═CHR⁴ or    —(CH₂)₇—CH═CH—(CH₂)₇—(CO)NH(CH₂)_(n)N(R²)R³.    General Note Regarding Chemical Structures:

As the skilled person will recognize, products made in accordance withthe invention are typically mixtures of cis- and trans-isomers. Exceptas otherwise indicated, all of the structural representations providedherein show only a trans-isomer. The skilled person will understand thatthis convention is used for convenience only, and that a mixture of cis-and trans-isomers is understood unless the context dictates otherwise.(The “C18-” series of products in the examples below, for instance, arenominally 100% trans-isomers whereas the “Mix-” series are nominally80:20 trans-/cis-isomer mixtures.) Structures shown often refer to aprincipal product that may be accompanied by a lesser proportion ofother components or positional isomers. For instance, reaction productsfrom modified triglycerides are complex mixtures. As another example,sulfonation or sulfitation processes often give mixtures of sultones,alkanesulfonates, and alkenesulfonates, in addition to isomerizedproducts. Thus, the structures provided represent likely or predominantproducts. Charges may or may not be shown but are understood, as in thecase of amine oxide structures. Counterions, as in quaternizedcompositions, are not usually included, but they are understood by theskilled person from the context.

Specific examples of C₁₀, C₁₂, C₁₄, and C₁₆-based fatty amines and fattyamidoamines appear below:

An exemplary C₁₈-based fatty amidoamine:

The fatty amine or fatty amidoamine product mixture can be complex whenthe ester derivative reacted with the amine or aminoalkyl-substitutedtertiary amine is a modified triglyceride made by self-metathesis of anatural oil and separation to remove olefins (see, e.g., the MTG andPMTG products described below) or an unsaturated triglyceride made bycross-metathesis of a natural oil and an olefin and separation to removeolefins (see, e.g., the UTG and PUTG products described below). As isevident from the reaction schemes, the MTG and PMTG products from DMAPAinclude an unsaturated C₁₈ diamidoamine as a principal component, whilethe UTG and PUTG products include a C₁₀ unsaturated amidoamine componentand one or more C₁₁ to C₁₇ unsaturated amidoamine components. (Forexample, with 1-butene as the cross-metathesis reactant, as illustrated,a C₁₂ unsaturated amidoamine component results.) Other components of theproduct mixtures are glycerin and saturated or unsaturated amides thatincorporate DMAPA. Despite the complexity, purification to isolate aparticular species is often neither economical nor desirable for goodperformance.

Thus, in one aspect, the fatty amidoamine is produced by reacting anaminoalkyl-substituted tertiary amine with a modified triglyceride madeby self-metathesis of a natural oil. Self-metathesis of the natural oilprovides a mixture of olefins and a modified triglyceride that isenriched in a C₁₈ unsaturated diester component along with C₁₆-C₁₈saturated diesters. The olefins are stripped out, usually with heat andreduced pressure. When the modified triglyceride is reacted directlywith DMAPA, a complex mixture results in which primary amino groups ofDMAPA completely or partially displace glycerin from the glyceryl estersto form amidoamine functionalities. Representative amidoamine productsbelow are made by reacting DMAPA with MTG-0 (modified triglyceride fromsoybean oil) or PMTG-0 (modified triglyceride from palm oil). Oneexample is the MTG DMAPA amide (“MTG-5”):

In another aspect, the fatty amidoamine is produced by reacting anaminoalkyl-substituted tertiary amine with an unsaturated triglyceridemade by cross-metathesis of a natural oil with an olefin.Cross-metathesis of the natural oil and olefin provides a mixture ofolefins and an unsaturated triglyceride that is rich in C₁₀ and C₁₂unsaturated esters as well as C₁₆-C₁₈ saturated esters. The olefins arestripped out, usually with heat and reduced pressure. When theunsaturated triglyceride is reacted directly with DMAPA, a complexmixture results in which primary amino groups of DMAPA completely orpartially displace glycerin from the glyceryl esters to form amidoaminefunctionalities. Representative amidoamine products below are made byreacting DMAPA with UTG-0 (unsaturated triglyceride fromcross-metathesis of soybean oil and 1-butene) or PUTG-0 (unsaturatedtriglyceride from cross-metathesis of palm oil with 1-butene). Oneexample is the PUTG DMAPA amide product (“PUTG-5”):

The reaction to form the amidoamines from lower alkyl esters can beperformed under a nitrogen sparge or under vacuum to remove liberatedalcohol. When glyceride esters are reactants, the liberated glycerinneed not be removed from the product. The reaction is consideredcomplete when the residual glyceride content of the product reaches thedesired level.

The invention includes derivatives made by one or more of oxidizing,sulfonating, and sulfitating the fatty amine or fatty amidoamine. Ifdesired, the carbonyl group of fatty amidoamines can also be reduced togive fatty amines.

Oxidation is accomplished by reacting the fatty amine or fattyamidoamine with on oxidant such as hydrogen peroxide, air, ozone,organic hydroperoxides, or the like, to covert a tertiary amine group toan amine oxide functionality according to well-known methods (seeMarch's Advanced Organic Chemistry, supra, at, p. 1541 and U.S. Pat. No.3,494,924). Exemplary procedures for oxidizing fatty amines or fattyamidoamines to the corresponding oxides using hydrogen peroxide alsoappear below.

Examples of suitable C₁₀, C₁₂, C₁₄, and C₁₆-based amine oxides:

An exemplary C₁₈-based amine oxide:

An exemplary amine oxide based on a PUTG-based amidoamine mixture(“PUTG-12”):

The fatty amines or amidoamines and their derivatives have unsaturationthat can be sulfonated or sulfitated if desired. Sulfonation isperformed using well-known methods, including reacting the olefin withsulfur trioxide. Sulfonation may optionally be conducted using an inertsolvent. Non-limiting examples of suitable solvents include liquid SO₂,hydrocarbons, and halogenated hydrocarbons. In one commercial approach,a falling film reactor is used to continuously sulfonate the olefinusing sulfur trioxide. Other sulfonating agents can be used with orwithout use of a solvent (e.g., chlorosulfonic acid, fuming sulfuricacid), but sulfur trioxide is generally the most economical. Thesultones that are the immediate products of reacting olefins with SO₃,chlorosulfonic acid, and the like may be subsequently subjected to ahydrolysis reaction with aqueous caustic to afford mixtures of alkenesulfonates and hydroxyalkane sulfonates. Suitable methods forsulfonating olefins are described in U.S. Pat. Nos. 3,169,142;4,148,821; and U.S. Pat. Appl. Publ. No. 2010/0282467, the teachings ofwhich are incorporated herein by reference.

Sulfitation is accomplished by combining an olefin in water (and usuallya cosolvent such as isopropanol) with at least a molar equivalent of asulfitating agent using well-known methods. Suitable sulfitating agentsinclude, for example, sodium sulfite, sodium bisulfite, sodiummetabisulfite, or the like. Optionally, a catalyst or initiator isincluded, such as peroxides, iron, or other free-radical initiators.Typically, the reaction mixture is conducted at 15-100° C. until thereaction is reasonably complete. Suitable methods for sulfitatingolefins appear in U.S. Pat. Nos. 2,653,970; 4,087,457; 4,275,013, theteachings of which are incorporated herein by reference.

The fatty amines, fatty amidoamines, and their oxidized, reduced,sulfonated, and sulfitated derivatives can be incorporated into manycompositions for use as, for example, surfactants, emulsifiers,skin-feel agents, film formers, rheological modifiers, biocides, biocidepotentiators, solvents, release agents, and conditioners. Thecompositions find value in diverse end uses, such as personal care(liquid cleansing products, conditioning bars, oral care products),household products (liquid and powdered laundry detergents, liquid andsheet fabric softeners, hard and soft surface cleaners, sanitizers anddisinfectants), and industrial or institutional cleaners.

The fatty amines or amidoamines and their derivatives can be used inemulsion polymerizations, including processes for the manufacture oflatex. They can be used as surfactants, wetting agents, dispersants, orsolvents in agricultural applications, as inert ingredients inpesticides, or as adjuvants for delivery of pesticides for cropprotection, home and garden, and professional applications. The fattyamines or amidoamines and their derivatives can also be used in oilfield applications, including oil and gas transport, production,stimulation and drilling chemicals, reservoir conformance andenhancement uses, and specialty foamers. The compositions are alsovaluable as foam moderators or dispersants for the manufacture ofgypsum, cement wall board, concrete additives and firefighting foams.The compositions are useful as coalescents for paints and coatings, andas polyurethane-based adhesives.

In food and beverage processing, the fatty amines or amidoamines andtheir derivatives can be used to lubricate the conveyor systems used tofill containers. When combined with hydrogen peroxide, the fatty aminesor amidoamines and their derivatives can function as low foamingdisinfectants and sanitization agents, odor reducers, and asantimicrobial agents for cleaning and protecting food or beverageprocessing equipment. In industrial, institutional and laundryapplications, the fatty amines or amidoamines and their derivatives, ortheir combination with hydrogen peroxide, can be used to remove soil andsanitize and disinfect fabrics and as antimicrobial film-formingcompositions on hard surfaces.

The following examples merely illustrate the invention. Those skilled inthe art will recognize many variations that are within the spirit of theinvention and scope of the claims.

Feedstock Syntheses Preparation of Methyl 9-Decenoate (“C10-0”) andMethyl 9-Dodecenoate (“C12-0”)

The procedures of U.S. Pat. Appl. Publ. No. 2011/0113679, the teachingsof which are incorporated herein by reference, are used to generatefeedstocks C10-0 and C12-0 as follows:

Example 1A

Cross-Metathesis of Soybean Oil and 1-Butene. A clean, dry,stainless-steel jacketed 5-gallon Parr reactor equipped with a dip tube,overhead stirrer, internal cooling/heating coils, temperature probe,sampling valve, and relief valve is purged with argon to 15 psig.Soybean oil (SBO, 2.5 kg, 2.9 mol, Costco, M_(n)=864.4 g/mol, 85 weight% unsaturation, sparged with argon in a 5-gal container for 1 h) isadded to the Parr reactor. The reactor is sealed, and the SBO is purgedwith argon for 2 h while cooling to 10° C. After 2 h, the reactor isvented to 10 psig. The dip tube valve is connected to a 1-butenecylinder (Airgas, CP grade, 33 psig headspace pressure, >99 wt. %) andre-pressurized to 15 psig with 1-butene. The reactor is again vented to10 psig to remove residual argon. The SBO is stirred at 350 rpm and9-15° C. under 18-28 psig 1-butene until 3 mol 1-butene per SBO olefinbond are transferred into the reactor (˜2.2 kg 1-butene over 4-5 h).

A toluene solution of[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]-dichlororuthenium(3-methyl-2-butenylidene)(tricyclohexylphosphine)(C827, Materia) is prepared in a Fischer-Porter pressure vessel bydissolving 130 mg catalyst in 30 g of toluene (10 mol ppm per mol olefinbond of SBO). The catalyst mixture is added to the reactor via thereactor dip tube by pressurizing the headspace inside the Fischer-Portervessel with argon to 50-60 psig. The Fischer-Porter vessel and dip tubeare rinsed with additional toluene (30 g). The reaction mixture isstirred for 2.0 h at 60° C. and is then allowed to cool to ambienttemperature while the gases in the headspace are vented.

After the pressure is released, the reaction mixture is transferred to around-bottom flask containing bleaching clay (Pure-Flo® B80 CG clay,product of Oil-Dri Corporation of America, 2% w/w SBO, 58 g) and amagnetic stir bar. The reaction mixture is stirred at 85° C. underargon. After 2 h, during which time any remaining 1-butene is allowed tovent, the reaction mixture cools to 40° C. and is filtered through aglass frit. An aliquot of the product mixture is transesterified with 1%w/w NaOMe in methanol at 60° C. By gas chromatography (GC), it contains:methyl 9-decenoate (22 wt. %), methyl 9-dodecenoate (16 wt. %), dimethyl9-octadecenedioate (3 wt. %), and methyl 9-octadecenoate (3 wt. %).

The results compare favorably with calculated yields for a hypotheticalequilibrium mixture: methyl 9-decenoate (23.4 wt. %), methyl9-dodecenoate (17.9 wt/%), dimethyl 9-octadecenedioate (3.7 wt. %), andmethyl 9-octadecenoate (1.8 wt. %).

Example 1B

The procedure of Example 1A is generally followed with 1.73 kg SBO and 3mol 1-butene/SBO double bond. An aliquot of the product mixture istransesterified with sodium methoxide in methanol as described above.The products (by GC) are: methyl 9-decenoate (24 wt. %), methyl9-dodecenoate (18 wt. %), dimethyl 9-octadecenedioate (2 wt. %), andmethyl 9-octadecenoate (2 wt. %).

Example 1C

The procedure of Example 1A is generally followed with 1.75 kg SBO and 3mol 1-butene/SBO double bond. An aliquot of the product mixture istransesterified with sodium methoxide in methanol as described above.The products (by GC) are: methyl 9-decenoate (24 wt. %), methyl9-dodecenoate (17 wt. %), dimethyl 9-octadecenedioate (3 wt. %), andmethyl 9-octadecenoate (2 wt. %).

Example 1D

The procedure of Example 1A is generally followed with 2.2 kg SBO and 3mol 1-butene/SBO double bond. Additionally, the toluene used to transferthe catalyst (60 g) is replaced with SBO. An aliquot of the productmixture is transesterified with sodium methoxide in methanol asdescribed above. The products (by GC) are: methyl 9-decenoate (25 wt.%), methyl 9-dodecenoate (18 wt. %), dimethyl 9-octadecenedioate (3 wt.%), and methyl 9-octadecenoate (1 wt. %).

Example 1E

Separation of Olefins from Modified Triglyceride. A 12-L round-bottomflask equipped with a magnetic stir bar, heating mantle, and temperaturecontroller is charged with the combined reaction products from Examples1A-1D (8.42 kg). A cooling condenser with a vacuum inlet is attached tothe middle neck of the flask and a receiving flask is connected to thecondenser. Volatile hydrocarbons (olefins) are removed from the reactionproduct by vacuum distillation. Pot temperature: 22° C.-130° C.;distillation head temperature: 19° C.-70° C.; pressure: 2000-160 μtorr.After removing the volatile hydrocarbons, 5.34 kg of non-volatileresidue remains. An aliquot of the non-volatile product mixture istransesterified with sodium methoxide in methanol as described above.The products (by GC) are: methyl 9-decenoate (32 wt. %), methyl9-dodecenoate (23 wt. %), dimethyl 9-octadecenedioate (4 wt. %), andmethyl 9-octadecenoate (5 wt. %). This mixture is also called “UTG-0.”(An analogous product made from palm oil is called “PUTG-0.”)

Example 1F

Methanolysis of Modified Triglyceride. A 12-L round-bottom flask fittedwith a magnetic stir bar, condenser, heating mantle, temperature probe,and gas adapter is charged with sodium methoxide in methanol (1% w/w,4.0 L) and the non-volatile product mixture produced in Example 1E (5.34kg). The resulting light-yellow heterogeneous mixture is stirred at 60°C. After 1 h, the mixture turns homogeneous and has an orange color(pH=11). After 2 h of reaction, the mixture is cooled to ambienttemperature and two layers form. The organic phase is washed withaqueous methanol (50% v/v, 2×3 L), separated, and neutralized by washingwith glacial acetic acid in methanol (1 mol HOAc/mol NaOMe) to pH=6.5.Yield: 5.03 kg.

Example 1G

Isolation of Methyl Ester Feedstocks. A 12-L round-bottom flask fittedwith a magnetic stirrer, packed column, and temperature controller ischarged with the methyl ester mixture produced in example 1F (5.03 kg),and the flask is placed in a heating mantle. The glass column is 2″×36″and contains 0.16″ Pro-Pak™ stainless-steel saddles (Cannon InstrumentCo.). The column is attached to a fractional distillation head to whicha 1-L pre-weighed flask is fitted for collecting fractions. Distillationis performed under vacuum (100-120 μtorr). A reflux ratio of 1:3 is usedto isolate methyl 9-decenoate (“C10-0”) and methyl 9-dodecenoate(“C12-0”). Samples collected during the distillation, distillationconditions, and the composition of the fractions (by GC) are shown inTable 1. A reflux ratio of 1:3 refers to 1 drop collected for every 3drops sent back to the distillation column. Combining appropriatefractions yields methyl 9-decenoate (1.46 kg, 99.7% pure) and methyl9-dodecenoate (0.55 kg, >98% pure).

TABLE 1 Isolation of C10-0 and C12-0 by Distillation Head Distillationtemp. Pot temp. Vacuum Weight C10-0 C12-0 Fractions # (° C.) (° C.)(μtorr) (g) (wt %) (wt %) 1 40-47 104-106 110 6.8 80 0 2 45-46 106 11032.4 99 0 3 47-48 105-110 120 223.6 99 0 4 49-50 110-112 120 283 99 0 550 106 110 555 99 0 6 50 108 110 264 99 0 7 50 112 110 171 99 0 8 51 114110 76 97 1 9 65-70 126-128 110 87 47 23 10 74 130-131 110 64 0 75 11 75133 110 52.3 0 74 12 76 135-136 110 38 0 79 13 76 136-138 100 52.4 0 9014 76 138-139 100 25.5 0 85 15 76-77 140 110 123 0 98 16 78 140 100 4260 100Precursor Syntheses:C10-25: C10 DMA Amide

A round-bottom flask is charged with methyl ester feedstock C10-0 (235g) and the mixture is degassed with nitrogen. Sodium methoxide (5 g of30% solution in methanol) is added via syringe and the mixture isstirred for 5 min. Dimethylamine (67 g) is slowly added via sub-surfacedip tube. After the addition, the mixture is heated to 60° C. and heldovernight. The amide, C10-25, is recovered via vacuum distillation (120°C., 20 mm Hg). Yield: 241.2 g (96.3%). Iodine value=128.9 g I₂/100 gsample. ¹H NMR (CDCl₃), δ (ppm)=5.8 (CH₂═CH—); 4.9 (CH₂═CH—); 2.8-3.0(—C(O)—N(CH₃)₂); 2.25 (—CH₂—C(O)—). Ester content (by ¹H NMR): 0.54%.

C12-25: C12 DMA Amide

A round-bottom flask is charged with methyl ester C12-0 (900 g) and thefeedstock is degassed with nitrogen at 60° C. Sodium methoxide (30 g of30% solution in methanol) is added via syringe and the mixture isstirred for 5 min. Vacuum is then applied and the reaction vesselsealed. Dimethylamine (200 g) is slowly added via sub-surface dip tubeagainst the static vacuum. After the addition, the remaining vacuum isreleased with nitrogen, and the mixture is heated to 70° C. for 1 h. Themixture is heated to 80° C., DMA is sparged through the liquid for 2 h,and the mixture is then heated to 90° C. for 1 h. The sparge is stopped,and the reaction is cooled to 75° C. Full vacuum is applied and held for0.5 h. The vacuum is released, and 50% H₂SO₄ (16.3 g) and deionizedwater (200 mL) are added to quench the catalyst. The organic layer iswashed with deionized water (2×300 mL, then 1×150 mL) and then 20% brinesolution (50 mL). The organic layer is concentrated (full vacuum, 75°C.) and vacuum distilled (pot: 140-150° C.) to isolate amide C12-25.Iodine value: 112.8 g I₂/100 g sample; % moisture: 65 ppm. ¹H NMR(CDCl₃), δ (ppm): 5.35 (—CH═CH—); 2.8-3.0 (—C(O)—N(CH₃)₂; 2.25(—CH₂—C(O)—).

Amine Syntheses:

C10-38: C10 Amine

Amide C10-25 (475 g) is slowly added over 3 h to a stirring THF slurryof LiAlH₄ (59.4 g) under nitrogen while maintaining the temperature at11-15° C. The mixture warms to room temperature and stirs overnight. Themixture is chilled in an ice bath, and water (60 g) is added cautiously,followed by 15% aq. NaOH solution (60 g) and then additional water (180g) is added. The mixture warms to room temperature and is stirred for 1h. The mixture is filtered, and the filter cake is washed with THF. Thefiltrates are combined and concentrated. NMR analysis of the crudeproduct indicates that it contains approximately 16% 9-decen-1-ol, aside-product formed during the reduction of the amide. In order tosequester the alcohol, phthalic anhydride is to be added, thus formingthe half-ester/acid. The product mixture is heated to 60° C. andphthalic anhydride (57.5 g) is added in portions. NMR analysis of themixture shows complete consumption of the alcohol, and the mixture isvacuum distilled to isolate C10-38. Amine value: 298.0 mg KOH/g; iodinevalue: 143.15 g 12/100 g sample; % moisture: 0.02%. ¹H NMR (CDCl₃), δ(ppm): 5.8 (CH₂═CH—); 4.9 (CH₂═CH—); 3.7 (—CH₂—N(CH₃)₂).

C12-26: C12 Amine

The procedure used to make C10-38 is generally followed with amideC12-25 (620 g) and LiAlH₄ (67.8 g). When the reaction is complete, water(68 g) and 15% aq. NaOH solution (68 g) and water (204 g) are used toquench the reaction. After the usual filtration and concentration steps,NMR analysis of the crude product shows approximately 16% 9-dodecen-1-olto be present. And phthalic anhydride (30 g) is added in order tosequester the alcohol. The mixture is then vacuum distilled to giveC12-26. Amine value: 258.1 mg KOH/g sample; iodine value: 120.0 g I₂/100g sample. ¹H NMR (CDCl₃), δ: 5.35 (—CH═CH—); 2.2 (—CH₂—N(CH₃)₂).

Amine oxides from Amines:

C10-39: C10 Amine Oxide

A round-bottom flask is charged with amine C10-38 (136 g), water (223g), and Hamp-Ex 80 (pentasodium diethylenetriamine pentaacetatesolution, 0.4 g). The mixture is heated to 50° C. and dry ice is addeduntil the pH is ˜7.0. When the pH stabilizes, hydrogen peroxide (35%solution, 73.5 g) is added dropwise, and the ensuing exotherm is allowedto heat the mixture to 75° C. When the peroxide addition is complete,the mixture is maintained at 75° C. for 18 h. Stirring continues at 75°C. until the residual peroxide level is <0.2%. ¹H NMR analysis indicatesa complete reaction, and the solution is cooled to room temperature togive amine oxide C10-39. Residual peroxide: 0.13%; free tertiary amine:0.63%; amine oxide: 32.6%.

C12-28: C12 Amine Oxide

A round-bottom flask equipped with an overhead mechanical stirrer andaddition funnel is charged with deionized water (93.5 g) and Hamp-Ex 80(0.3 g). The mixture is heated to 50° C. while amine C12-26 (137 g, 0.65mol) and dry ice (˜5 g) are added. Hydrogen peroxide (35% solution, 64.3g, 0.66 mol) is added dropwise to the reaction mixture, allowing themixture to exotherm to 80° C. and then controlling the reaction at thistemperature using a water bath for cooling. The mixture thickens aftertwo-thirds of the H₂O₂ has been added, and more deonized water (73.7 g)is added. After completing the peroxide addition, the mixture stirs at80° C. for 24 h until a peroxide test strip indicates low residualperoxide. The ˜40% solids reaction mixture is diluted with water to˜37.5% solids to afford a homogenous solution. Titration shows 37.2% C12amine oxide and 0.009% free amine. Analysis by ¹H NMR (CDCl₃) confirmsthe formation of the amine oxide, based on shift of the N(CH₃)₂ peakfrom 2.18 ppm (for the amine) to 3.12 ppm.

Amidoamine Syntheses:

C10-17: C10 DMAPA Amide

A round-bottom flask equipped with nitrogen sparge tube, mechanicalstirrer, and Dean-Stark trap is charged with methyl ester C10-0 (500 g,2.7 mol), 3-(dimethyl-amino)propylamine (“DMAPA,” 331 g, 3.24 mol), andsodium methoxide (8.3 g of a 30% solution of in methanol). The reactionmixture is heated to 100° C. and methanol is collected. The reactiontemperature is increased in 5° C. increments until the temperaturereaches 130° C. The mixture is held at 130° C. for 1 h, and then asub-surface nitrogen sparge is applied for 2.5 h. The temperature iselevated to 140° C. for an additional 3.5 h. Collected distillate (122mL) includes methanol and some DMAPA. The reaction mixture is cooled to110° C., the nitrogen sparge is discontinued, and vacuum was applied.The mixture is stripped of excess DMAPA (150° C., 20 mm Hg, 30 min.).The product, amidoamine C10-17, has an amine value of 224.14 (eq. wt.:250.28). ¹H NMR (CDCl₃) confirms formation of the amide, based ondisappearance of the methyl ester peak at 3.61 ppm and appearance of theDMAPA CH₂ signals at 3.27, 2.09, and 1.60 ppm and the N(CH₃)₂ at 2.18ppm.

C12-17: C12 DMAPA Amide

The procedure used to make C10-17 is generally followed with methylester C12-0 (670 g), DMAPA (387 g), and sodium methoxide (11.2 g of 30wt. % solution in methanol). The resulting product, amidoamine C12-17,has an amine value of 196.39 (eq. wt.: 281.3). ¹H NMR (CDCl₃) confirmsformation of the amide, based on disappearance of the methyl ester peakat 3.61 ppm and appearance of the DMAPA CH₂ signals at 3.30, 2.11, and1.62 ppm and the N(CH₃)₂ at 2.20 ppm.

Amine Oxides from Amidoamines:

C10-20: C10 DMAPA AO

A round-bottom flask is charged with amidoamine C10-17 (162.6 g), water(267 g), and Hamp-Ex 80 (0.5 g). The mixture is heated to 50° C. undernitrogen and several small pieces of dry ice are added. Hydrogenperoxide (35 wt. % aqueous solution, 64.5 g) is added dropwise whilekeeping the temperature less than 75° C. After completing the H₂O₂addition, the mixture is maintained at 70° C. for 7 h. Peroxide papertest indicates <0.5% residual H₂O₂. The mixture is heated for 3 h at 75°C. and then cooled to room temperature to give amine oxide C10-20 inwater. The product comprises (by titration): 35.2% amine oxide; 0.85%free amine.

C12-20: C12 DMAPA AO

A round-bottom flask is charged with amidoamine C12-17 (250 g), water(400 g), and Hamp-Ex 80 (0.7 g). Dry ice is added until the pH is 8-9.The mixture is heated to 50° C. under nitrogen. Hydrogen peroxide (35wt. % solution, 88 g) is added dropwise while maintaining thetemperature at less than 75° C. The mixture is maintained at 70° C. for3 h, then cooled to room temperature overnight. The mixture is reheatedto 75° C. and water (50 g) is added to help dissolve solids. The mixtureis held at 75° C. for 4 h. Analysis with peroxide test strips indicatestrace residual peroxide. The mixture is cooled to recover amine oxideC12-20 as an aqueous solution. The product comprises (by titration):33.4% amine oxide; 0.06% free amine.

Sulfonated Derivatives from Amidoamines:

C10-21: C10 DMAPA AO Sulfonate

A round-bottom flask equipped with stir bar, condenser, and thermocoupleis charged with amine oxide C10-20 (212.4 g, 36.8% solids) and sodiummetabisulfite (Na₂S₂O₅; 28.09 g, 1.03 eq. NaHSO₃), and this mixture isstirred until homogeneous. The solution is heated to 80° C. and the pHis adjusted to 7.5 with SO₂ gas. After 30 min., the pH is adjusted againwith SO₂ to 7.5. After 1 h, the pH is adjusted a third time with SO₂ andis then heated at 80° C. overnight. After 16 h, ¹H NMR analysis (D₂O)indicates a complete reaction. The signal for the amine oxide methylgroup had shifted to 2.6 ppm (from 3.1 ppm in the starting material),indicating conversion of amine oxide to sulfitoamine. Sodium hydroxide(5.46 g, 0.2 eq.) is added to hydrolyze the sulfitoamine and the mixtureis heated at 80° C. overnight. After 16 h, ¹H NMR analysis indicatesthat the amine methyl signal has shifted to 2.2 ppm, indicatinghydrolysis of sulfitoamine to the corresponding amine. The mixture iscooled to 50° C. and the pH is adjusted from 10.1 to 8.3 by adding dryice. Hydrogen peroxide (28.43 g, 1.02 eq.) is added dropwise,maintaining the reaction temperature below 70° C. The mixture ismaintained at 70° C. for 16 h. The mixture is cooled to providesulfonate C10-21 as an aqueous solution. Analysis by ¹H NMR (D₂O)confirms formation of the amine oxide sulfonate, based appearance of theN(CH₃)₂ at 3.2 ppm, which matches up well with the N(CH₃)₂ in thestarting amine oxide, and a new signal at 2.7 ppm corresponding to theprotons adjacent to the sulfonate group (—CH₂SO₃Na).

C12-42: C12 DMAPA Sulfonate

Amidoamine C12-17 (193.7 g) and isopropyl alcohol (“IPA,” 400 g) arecharged to a flask equipped with a mechanical stirrer and athermocouple. A solution prepared from sodium metabisulfite (65.5 g),sodium sulfite (8.4 g), and deionized water (400 g) is added. Themixture is heated to 75° C., and the pH is adjusted from 7.5 to 6.5 withSO₂ gas. tert-Butylperoxybenzoate (TBB, 1 mL) is added. Over the next 16h, additional water (200 g), IPA (100 g), and TBB (2.2 mL) are added.The pH is adjusted three additional times with SO₂ to 6.5. Upon cooling,the reaction mixture is stripped to remove IPA, and the pH of the liquidproduct is adjusted to 9.0 by adding NaOH. The aqueous sulfonatedproduct (982 g) is analyzed. ¹H NMR (D₂O) indicates 80% conversion ofstarting olefin based on integration of residual olefin proton signalsat 5.2-5.5 ppm. Formation of the sulfonated product is confirmed by thepresence of a new signal at 2.4-2.6 ppm, corresponding to the protonadjacent to the sulfonate. The product comprises, in addition to thesulfonate, 60.1% water, 3.63% IPA, 5.15% Na₂SO₄, and 1.99% Na₂SO₃.

C12-21: C12 DMAPA AO Sulfonate

Sulfonate C12-42 (405.5 g) and Hamp-Ex 80 (0.37 g) are charged to around-bottom flask. The mixture is heated to 50° C. and aqueous hydrogenperoxide (35%, 46.65 g) is added dropwise without additional heating,maintaining the reaction temperature below 75° C. The mixture ismaintained at 85° C. for 36 h. Sodium thiosulfate titration indicatesthat the product contains 0.9% residual hydrogen peroxide. Watercontent: 63.93%. ¹H NMR (D₂O) indicates 70% conversion of startingtertiary amine to the amine oxide, based on integration of the N(CH₃)₂peaks at 2.74 ppm, for the amine, to 3.25 ppm, for the amine oxide.

Preparation of Methyl 9-Hexadecenoate (“C16-0”) Feedstock

The procedures of Example 1A is generally followed except that 1-octeneis cross-metathesized with soybean oil instead of 1-butene. Combinedreaction products are then stripped as described in Example 1E to removethe more volatile unsaturated hydrocarbon fraction from the modified oilfraction. The procedure of Example 1F is used to convert the modifiedoil fraction to a methyl ester mixture that includes methyl9-hexadecenoate. Fractional distillation at reduced pressure is used toisolate the desired product, methyl 9-hexadecenoate from other methylesters.

C16-9: C16 DMAPA Amide:

A round-bottom flask equipped with nitrogen sparge tube, mechanicalstirrer, and Dean-Stark trap is charged with methyl ester C16-0 (505.2g), DMAPA (223.2 g), and sodium methoxide (12.6 g of a 30% solution ofin methanol). The reaction mixture is heated to 105° C. and methanol iscollected. The reaction temperature is increased gradually until thetemperature reaches 140° C. The mixture is held at 140° C. for 2 h. Thereaction mixture is cooled to 100° C., and vacuum is applied, withtemperature gradually increased to 120° C. Analysis after a weekend atroom temperature shows a complete reaction. Residual DMAPA is stripped(130° C., full vacuum, 3 h). The product, amidoamine C16-9, has eq. wt.:339.5, free DMAPA: 0.56%, and a ¹H NMR spectrum consistent with theexpected structure.

C16-11: C16-DMAPA Sulfonate:

Amide C16-9 (228.4 g) is charged to a round-bottom flask equipped withan agitator, condenser, and thermocouple, and isopropyl alcohol (IPA,530 g) is added. Sodium sulfite (33.6 g) is dissolved in water and addedto the amide solution, followed by tert-butylperoxybenzoate (TBB, 1.3g). The mixture is heated to 75° C., and the pH is adjusted from 8.2 to6.9 with SO₂. The pH rises over the first 4 h and is adjusted down to6.9 with SO₂. The mixture stirs overnight. The remaining sodium sulfite(33.6 g) is added and no pH adjustment is needed. More TBB (1.3 g) isadded and the reaction mixture stirs overnight at 75° C. 1H NMR analysisshows 50% conversion. The pH is adjusted from 6.5 to 6.7, more TBB (1.0mL) is added, and the mixture stirs overnight at 75° C. Conversionreaches 63%, and a significant amount of SO₂/SO₃ remains, so the pH isadjusted to 6.8 and stirring continues. Prolonged heating fails tosignificantly improve conversion, and the reaction is discontinued. IPAand water are stripped to give C16-11 as a solution of 48% solids.Moisture: 52.1%; pH: 6.34; inorganic sulfate: 7.43%; Na₂SO₃: 3.45%;conversion of C16-9 to sulfitated amidoamine (by ¹H NMR): 67.5%.

C16-12: C16 DMAPA Sulfonate AO

A round-bottom flask is charged with DMAPA sulfonate C16-11 (442.3 g),water (490 g), and Hamp-Ex 80 (1.3 g). Hydrogen peroxide (35% solution,106 g) is added dropwise, keeping the temperature below 75° C. byexternal cooling as needed. At the end of the addition, the mixture isheld at 75° C. for 18 h. Analysis of the mixture by thiosulfatetitration shows a high level of residual peroxide, and stirringcontinues at 75° C. until the level is <1%. The solution is cooled toroom temperature and the amine oxide product, C16-12, is analyzed. The¹H NMR spectrum is consistent with the target structure and shows noresidual free amine.

Feedstock Synthesis Preparation of Dimethyl 9-Octadecene-1,18-dioate(“Mix-0” or “C18-0”)

Eight samples of methyl 9-dodecenoate (10.6 g each, see Table 2) arewarmed to 50° C. and degassed with argon for 30 min. A metathesiscatalyst([1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichlororuthenium(3-methyl-2-butenylidene)-(tricyclohexylphosphine),product of Materia) is added to the methyl 9-dodecenoate (amountindicated in Table 2) and vacuum is applied to provide a pressure of <1mm Hg. The reaction mixture is allowed to self-metathesize for the timereported. Analysis by gas chromatography indicates that dimethyl9-octadecene-1,18-dioate is produced in the yields reported in Table 2.“Mix-0” is an 80:20 trans-/cis-isomer mixture obtained from the reactionmixture. Crystallization provides the all-trans-isomer feed, “C18-0.”

TABLE 2 Self-Metathesis of Methyl 9-Dodecanoate Catalyst LoadingReaction C18-0 Sample (ppm mol/mol)* Time (h) (GC Area %) A 100 3 83.5 B50 3 82.5 C 25 3 83.0 D 10 3 66.2 E 15 4 90.0 F 13 4 89.9 G 10 4 81.1 H5 4 50.9 *ppm mol catalyst/mol methyl 9-dodecenoateC18 Dibasic Acid Derivatives:C18-26: C18 DiDMAPA Amide (100% trans-)

A round-bottom flask equipped with a mechanical stirrer is charged withdiester C18-0 (545.6 g) and DMAPA (343.3 g). A Dean-Stark trap isattached, and sodium methoxide (20 g of 30 wt % solution in MeOH) isadded. The temperature is raised to 110° C. over 1.5 h, and methanol iscollected. The temperature is increased to 150° C. in increments as thedistillation slows. The mixture is held at 150° C. for 6.5 hours andthen cooled to room temperature. ¹H NMR analysis indicates a minoramount of unreacted methyl ester. The mixture is heated to 180° C. forseveral hours and additional DMAPA and sodium methoxide are added. Themixture is cooled and neutralized with concentrated hydrochloric acid.When the mixture has cooled to 90° C., deionized water is added slowlywith vigorous agitation, resulting in precipitation of the amide toafford a slurry. Solids are isolated by vacuum filtration and washedwith water. The solid product, all-trans amide C18-26, is dried undervacuum. Yield: 92.2%. ¹H NMR (CDCl₃) confirms formation of the amide,based on disappearance of the methyl ester peak at 3.65 ppm andappearance of the DMAPA CH₂ signals at 3.31, 2.12, and 1.62 ppm and theN(CH₃)₂ at 2.20 ppm.

MIX-26: C18 DiDMAPA Amide (80:20 trans-/cis-)

The procedure used to make C18-26 is generally followed with diesterMix-0 (824.3 g), DMAPA (519.5 g), and sodium methoxide (20 g of 30 wt %solution in MeOH). The temperature is increased to 140° C. and held forseveral hours with a slow nitrogen sparge to assist in removingvolatiles. ¹H NMR analysis shows only a trace of starting ester. Themixture is cooled to 100° C. and dried under full vacuum. The mixture isthen neutralized with sulfuric acid (50%, 11 g) and deionized water isadded, resulting in precipitation of amide product. The product isvacuum filtered and washed with water. The filtrate is extracted with amixture of chloroform and ethyl acetate. The organic solvent isevaporated to afford a yellow oil that solidifies upon standing. Theoily solids and solids obtained by filtration are combined and dissolvedin chloroform. The chloroform is evaporated under reduced pressure andthe resulting solid is dried under high vacuum. The product, Mix-26, hasan amine value of 229.14 (eq. wt.: 489.7). ¹H NMR (CDCl₃) confirmsformation of the amide, based on disappearance of the methyl ester peakat 3.61 ppm and appearance of the DMAPA CH₂ signals at 3.31, 2.12, and1.63 ppm and the N(CH₃)₂ at 2.21 ppm.

C18-29: C18 DiDMAPA DiAO (100% trans-)

A round-bottom flask is charged with amine C18-26 (141.0 g), water(231.2 g), and Hamp-Ex 80 (0.4 g). The mixture is heated to 50° C. anddry ice is added to pH 8.8. When the pH stabilizes, aqueous H₂O₂ (35%,57.8 g) is added dropwise without heating, keeping the temperature below75° C. After the peroxide addition is complete, the mixture is warmed at85° C. for 18 h. The mixture is cooled to room temperature. Titrationsreveal: amine oxide: 1.32 meq/g; free amine: 0.027 meq/g; free peroxide:0.0019%; water: 66.4%.

MIX-29: C18 DiDMAPA DiAO (80:20 trans-/cis-)

The procedure used to make C18-29 is generally followed with amineMix-26 (140.0 g), water (230 g), Hamp-Ex 80 (0.4 g), and 35% hydrogenperoxide (57.2 g). Thereafter, titrations indicate: amine oxide: 1.33meq/g; free amine: 0.046 meq/g; free peroxide: 0.10%; and water: 64.24%.

C18-30: C18 DiDMAPA DiAO Sulfonate

Unsaturated diamide C18-26 (115.38 g) is heated to 60° C. with isopropylalcohol (700 g) in a round-bottom flask to dissolve the startingmaterial, and t-butylperoxybenzoate (1.25 mL) is added. A solution madefrom sodium metabisulfite (12.99 g), sodium sulfite (1.67 g), anddeionized water (500 g) is added dropwise over 15 min. to the olefinsolution. The reaction mixture is stirred at 75° C., the pH is adjustedfrom 9.0 to 6.5 with SO₂, and the mixture is maintained at 75° C. for 16h. ¹H NMR analysis shows 54% conversion. The pH is adjusted with SO₂ to6.5 three more times over the next 8 h, and the mixture is then stirredat 75° C. for 16 h. After stripping away solvent, the ¹H NMR showsnegligible residual IPA, and integration of the olefin peaks indicatesthat the mixture is 77% sulfitated product and 23% starting olefin.

The mixture is transferred to a round-bottom flask. Hamp-Ex 80 (0.32 g)is added, and the resulting solution is heated to 50° C. Aqueous H₂O₂(35%, 47.3 g) is added dropwise without heating, keeping the temperaturebelow 75° C. After the peroxide addition is complete, the mixture iswarmed at 85° C. for 18 h. The product is cooled to room temperature andanalyzed. Titrations show: free peroxide: 0.25%; water: 63.71%. ¹H NMR(D₂O) indicates complete conversion of the starting diDMAPA amide to theexpected amine oxide product as evidenced by disappearance of theN(CH₃)₂ peak at 2.20 ppm for the amine and appearance of a peak at 2.73ppm for the amine oxide N(CH₃)₂.

MIX-69: C18 Ester/Acid (80:20 trans-/cis-)

The half-acid/ester Mix-69 is prepared from the dibasic ester Mix-0(used as received) as described in Organic Syntheses: Col. Vol. IV(1963) 635. Thus, Mix-0 (1 kg) is added to methanol (˜9 L) and themixture is stirred mechanically. In a separate vessel, Ba(OH)₂ (274.4 g)is dissolved in methanol (˜4 L), and the solution is added in portionsover 2 h to the stirred diester solution, resulting in the formation ofa white precipitate. The solid is isolated by filtration, washed severaltimes with methanol, and dried in air. The solid is then transferred toa 12-L reaction vessel and slurried in ethyl acetate (˜3.5 L). AqueousHCl (32%, Aldrich, 1248.6 g), is added in portions to the stirredslurry, resulting in dissolution of the solid and formation of a clearsolution. The solution is washed three times with water, and the aqueouslayers are removed and collected in a separate vessel. The combinedaqueous layers are extracted once with ethyl acetate, and the organicphase is combined with the washed product solution. The mixture is dried(Na₂SO₄), filtered, and concentrated via rotary evaporator. Thoroughdrying under high vacuum gives a waxy, crystalline solid upon cooling(655 g, ˜70% yield). Analysis of the product (following derivatization)by gas chromatography shows that it contains 94% acid/ester and 6%diacid. Quantitative ¹³C NMR shows an 86:14 trans:cis isomer ratio.

MIX-43: C18 Ester/DMAPA Amide (80:20 trans-/cis-)

The mixed acid/ester Mix-69 is converted to the acid chloride/ester byreaction with a slight excess of thionyl chloride (SOCl₂) in methylenechloride solution and the product is isolated by removal of the solventand excess SOCl₂ under reduced pressure. ¹H NMR analysis of the isolatedproduct shows essentially quantitative conversion to the acidchloride/ester, and the material is used without further purification.

A 3-L reaction vessel equipped with mechanical stirrer, nitrogen inlet,and thermocouple is charged with methylene chloride (200 mL), DMAPA(172.1 g), and pyridine (133.3 g). The previously prepared acidchloride/ester is added dropwise to the stirred DMAPA-pyridine solution.During the addition, the temperature is maintained at 25-40° C. bycooling with an ice bath as required, and the addition is completed in1.5 h. A precipitate forms, and after stirring overnight at roomtemperature, the mixture has become a thick slurry. The mixture isdiluted with methylene chloride (500 mL), and water (500 mL) is added,giving a clear homogeneous solution. Addition of ethyl acetate fails toinduce phase separation. However, addition of saturated NaCl solutioncauses slow separation of a lower aqueous phase, which is drained anddiscarded. Concentration of the organic phase via rotary evaporationgives a viscous brown oil. ¹H NMR analysis shows free pyridine andindicates that the terminal tertiary amine of the DMAPA moiety isprotonated. The material is taken up in acetone and the mixture isfiltered to remove a small quantity of precipitated solid. The pH of thesolution is adjusted to ˜8.5 (measured on as-is material) with 50% aq.NaOH, resulting in the formation of a solid precipitate. The mixture isfiltered again and the clear filtrate is concentrated and then driedunder high vacuum. On cooling, the material solidifies. ¹H NMR analysisis consistent with the target structure and shows the presence of freepyridine. The product is heated to 60° C., stirred, and sparged withsub-surface nitrogen under reduced pressure for 5 h, then at 105° C. for30 min. After stripping, ¹H NMR analysis of the product showed noresidual pyridine.

MIX-46: C18 Ester DMAPA AO (80:20 trans-/cis-)

A round-bottom flask fitted with a thermocouple and overhead stirrer ischarged with ester-amide Mix-43 (140 g) that has been melted at 50° C.,water (240 g), and Hamp-Ex 80 (0.50 g). The mixture is warmed to 50° C.and hydrogen peroxide (33.82 g of 35% aq. solution) is added dropwise.During the addition, the mixture exotherms, and temperature is keptbelow 75° C. The mixture is stirred at 70° C. for 4 h. Additionalhydrogen peroxide solution (1.0 g) is added, and the mixture stirs at70° C. for an additional 2 h. The product gives a satisfactory ¹H NMRspectrum, free amine, and residual peroxide results. The pH is increasedfrom 6.8 to >8 by adding 50% aq. NaOH (3 g). Analysis shows: moisture:64.2%; free tertiary amine: 0.15%; amine oxide: 27.5%; residualperoxide: 0.36%.

C18-68: C18 diDMAPA Amide Sulfonate (100% trans-)

DiDMAPA amidoamine C18-26 (82.9 g) is added to isopropyl alcohol (IPA,500 g), and the mixture is heated to 60° C. and stirred, giving ahomogeneous solution. Sodium sulfite (9.3 g) is dissolved in water (250g), and the solution is added to the amidoamine solution. The pH isadjusted from 9.2 to 6.5 with gaseous SO₂ and t-butylperoxybenzoate(TBB, 0.90 mL) is added. The mixture is stirred at 75° C., and more IPA(50 g) is added to help solubility. Eventually, the mixture thickens andmore IPA (50 g) and water (50 g) are added. The mixture stirs overnight.Water (75 g) and more TBB (0.25 mL) are added to the cloudy mixture.Analysis by ¹H NMR after several hours indicates 50% conversion. Themixture stirs overnight, and further analysis shows 59% conversion. Aslow O₂ sparge is introduced to drive off IPA and the temperature israised to 80° C. After approximately 6 h, heating is discontinued andthe mixture stirs at room temperature over the weekend. Analysis shows97% conversion. Residual IPA is stripped to give the sulfonate, C18-68.Moisture: 62.6%; inorganic sulfate: 7.28%.

MIX-70: C18 Na Carboxylate/DMAPA Amide (80:20 trans-/cis-)

The methyl ester/DMAPA amide Mix-43 (276.8 g) and methanol (500 mL) arecharged to a flask equipped with thermocouple, mechanical stirrer, andreflux condenser. The mixture is stirred and heated to 70° C. Duringheat-up, dropwise addition of NaOH (50% aq. solution, 64.4 g) commences,causing the mixture to thicken to a pasty consistency. When 70° C. isreached and the addition completed, the mixture has become a pastysuspension. The mixture is heated to reflux under nitrogen and held for3 h. A small aliquot is removed, the volatiles removed under reducedpressure, and the resulting solid analyzed by ¹H NMR, which revealscomplete consumption of the starting methyl ester. The mixture iscooled, stripped via rotary evaporator, and dried under high vacuumovernight. ¹H NMR analysis shows residual MeOH, and the product is takenup in water (900 g) and subjected to rotary evaporation until ¹H NMRanalysis shows no remaining MeOH. The NMR spectrum is consistent withthe target structure. Analysis shows: pH (as-is): 12.8; amine value:72.3 meq/g; moisture: 72.6%.

MIX-73: C18 Carboxylate DMAPA AO (80:20 trans-/cis-)

An aqueous solution of carboxylate-DMAPA amide Mix-70 (758.2 g of a 24%actives solution) is charged to a flask equipped with mechanicalstirrer, thermocouple, reflux condenser, and nitrogen inlet. The mixtureis warmed to 60° C. and hydrogen peroxide (35% aq. solution, 50.7 g) isadded dropwise. The mixture foams up into the condenser, so peroxideaddition and agitation are discontinued. The mixture is transferred to3-L flask and heated to 60° C. The peroxide addition is completed,resulting in a significant lightening of the color. Additional hydrogenperoxide solution (11.6 g) is added, and the mixture is stirred 30 min.,then cooled to room temperature overnight. NMR analysis shows incompleteconversion. The mixture is reheated to 60° C. and more hydrogen peroxideis added in portions until conversion is satisfactory. Analysis of theamine oxide, Mix-73, shows: moisture: 79.4%; residual peroxide: 0.03%.

Modified Triglyceride Based on Soybean Oil (“MTG-0”)

The procedures of Examples 1A and 1E are generally followed except that1-butene is omitted.

Mod. Triglyceride From Cross-Metathesis of Soybean Oil and 1-Butene(“UTG-0”)

The procedures of Examples 1A and 1E are generally followed to produceUTG-0 from soybean oil and 1-butene.

Modified Triglyceride Based on Palm Oil (“PMTG-0”)

The procedure used to make MTG-0 is followed, except that palm oil isused instead of soybean oil.

Mod. Triglyceride From Cross-Metathesis of Palm Oil and 1-Butene(“PUTG-0”)

The procedure used to make UTG-0 is followed, except that palm oil isused instead of soybean oil.

MTG-0 Feedstock Derivatives

TABLE 3 Summary of Modified Triglyceride Products Soybean Oil Palm OilSelf-met. X-met. Self-met. X-met. MTG-0 UTG-0 PMTG-0 PUTG-0 DMAPA AmideMix MTG-5 UTG-5 PMTG-5 PUTG-5 DMAPA AO MTG-12 UTG-12 PMTG-12 PUTG-12DMAPA = N,N-dimethyl-1,3-propanediamine.

Detailed procedures appear below for preparation of the MTG and PUTGproducts starting from MTG-0 or PUTG-0. The PMTG products have analogousstructures to the MTG products. The UTG products have structuresanalogous to the PUTG products.

MTG-5: MTG DMAPA Amide Mix

A round-bottom flask is charged with MTG-0 (180 g, saponificationvalue=226.5 mg KOH/g, 0.73 mol), and the contents are heated to 50° C.The mixture is purged with nitrogen for 1 h and dimethylaminopropylamine(DMAPA, 78 g, 0.76 mol) and NaBH₄ (0.1 g) are added. The mixture isheated to 160° C. for 18 h. Excess amine is removed by short-pathdistillation (135° C., 30 mm Hg), and the product is cooled to roomtemperature to afford amidoamine mixture MTG-5. Amine value: 172.9 mgKOH/g (eq. wt.: 324.45 g/mol). Free DMAPA: 1.80%; iodine value: 71.9 g12/100 g sample.

MTG-12: MTG DMAPA AO

Molten MTG-5 (145.5 g, 0.42 mol) and deionized water (303.7 g) arecharged to a reaction flask equipped with reflux condenser, additionfunnel, thermocouple, mechanical stirrer, and nitrogen inlet. Thereactor contents are heated to 40° C. with stirring. Dry ice is added insmall pieces resulting in a homogeneous solution. Thereafter, 35% H₂O₂(43.4 g, 0.47 mol) is added over 15 min., and the reaction temperatureincreases to 69° C. The initially viscous solution becomes thinner asmore peroxide is added. When peroxide addition is complete, the mixtureis cooled to 65° C. and allowed to stir for 4 h. Free peroxide: <2 mg/L.The reaction mixture cools to room temperature and stands overnightunder a nitrogen purge. The product mixture shows no measurableperoxide. Additional 35% H₂O₂ solution (2.15 g) is added, and themixture is heated to 65° C. for 4 h. Upon cooling, analysis of theMTG-12 product shows: pH (10% aqueous): 7.44; water: 69.5%; free amine:1.52%; amine oxide actives: 29.1%; hydrogen peroxide: 0.01%.

PUTG-5: PUTG DMAPA Amide Mix

Molten PUTG-0 (750 g, saponification value: 227.6 mg KOH/g, 3.04 mol) ischarged to a reaction vessel equipped with a reflux condenser,thermocouple, nitrogen/vacuum take-off, and mechanical agitator. Themixture is stirred at 60° C. under nitrogen. Sodium borohydride (0.4 g)is added, and the mixture is stirred for 0.5 h. The mixture is degassedunder full vacuum (0.5 h). The vacuum is released with nitrogen anddimethylaminopropylamine (DMAPA, 325 g, 3.18 mol) is then added. Thetemperature is increased until a gentle reflux of DMAPA occurs (˜150°C.). The mixture is held at 150° C. until reflux slows. The temperatureis then increased to 160° C. Stirring continues for 4 h at 160° C., andthen the mixture is stirred overnight at 150° C. The mixture is cooledto 100° C. and excess DMAPA is removed using a gentle vacuum and dry-icetrap. Vacuum is slowly improved until full vacuum is reached. Strippingcontinues for 1 h. The waxy product, PUTG-5, is titrated with HCl. Acidvalue: 160.6 meq/g; eq. wt.: 349.4 g/mol. Amine value: 160.56 mg KOH/g;% free DMAPA: 0.08%. ¹H NMR (CDCl₃), δ: 5.8 (CH₂═CH—); 5.4 (—CH═CH—);4.9 (CH₂═CH—); 3.2 (—C(O)—NH—CH₂—); 2.15 (—N(CH₃)₂)

PUTG-12: PUTG DMAPA AO

Molten PUTG-5 (191.2 g; 0.55 mol) is charged to a reaction vessel, andwater (325 g) and Hamp-Ex 80 (0.5 g) are then added. The mixture isstirred mechanically, warmed to 50° C., and the headspace is flushedwith nitrogen for 0.5 h. Several pieces of dry ice are added, and themixture stirs for 15 min. Hydrogen peroxide solution (54.3 g of 35%solution, 0.56 mol) is then added dropwise. The ensuing exotherm beginsquickly and is allowed to heat the mixture to 70° C. When the additionof H₂O₂ is complete, the mixture is held at 70° C. for 4 h and thencooled to room temperature overnight. The mixture is reheated to 40° C.,and the reaction is judged complete based on a residual peroxide test.¹H NMR spectrum of dried material is consistent with the targetstructure. The liquid product, PUTG-12, is then analyzed to give: pH(10% aqueous): 7.72; amine oxide actives: 35.6%; free amine: 1.09%;peroxide: 0.12%.

Agricultural Glyphosates: Formulation Stability

Sample Preparation:

A 44.0% acid equivalent (a.e.) formulation is prepared by first chargingglyphosate acid (486.2 g, 90.5% a.e., product of Monsanto) to anice-cooled 1-L reaction vessel equipped with a mixer and temperatureprobe. Deionized water (337.2 g) is added with mixing to generate aglyphosate acid slurry. Potassium hydroxide pellets (176.6 g, 86.6% KOH,Fisher) are slowly added such that the temperature of the solution doesnot exceed 50° C. The mixture is then allowed to cool to roomtemperature and is mixed until a clear glyphosate concentrate of 44%a.e. results.

Stability Testing:

A test surfactant (5.0 g) is added to 45.0 g of the glyphosateconcentrate above (44% a.e.) to yield a glyphosate formulationconcentrate, ˜39.6% a.e. (˜540 g/L a.e. K salt). This concentrate ismixed until a clear solution results. If no clear solution results, analiquot of lauryl dimethyl amine oxide (LDMAO, ˜50-60% actives, productof Stepan) is added to the surfactant to make a 90:10 surfactant:LDMAOblend. This is then tested for stability as above. If that does notpass, the procedure of adding LDMAO to the surfactant continues until aratio is found that gives a stable glyphosate formulation. If no stableformulation can be made, the surfactant is deemed incompatible withglyphosate. If a clear homogeneous solution results, the sample is splitin two and placed both in a 54° C. oven and a −10° C. freezer for twoweeks. If there is no haziness or separation, the formulation isconsidered stable at that temperature.

The control surfactant is a C₁₂-C₁₄ DMEA esterquat. This is prepared byreacting a mixture of lauric (C₁₂) and myristic (C₁₄) acids withN,N-dimethylethanolamine (DMEA) at 140° C. for 5 h, then heating to 175°C. to complete the reaction. Quaternization with methyl chloride inpropylene glycol at 80° C. at 40 psig in the usual way provides thedesired esterquat. The control surfactant gives a clear formulation atroom temperature but the formulation separates at −10 C. Addition ofamine oxide in a 9:1 to 1:1 ratio (control surfactant to amine oxide) isneeded to give a desirable stability with the control.

As shown in Table 4, eight samples provided superior performance andseven performed as well as similar compounds in the stability testing.

TABLE 4 Glyphosate Formulation Stability: 540 g.a.e./L K salts AO Stableat: Sample added RT −10° C. 54° C. Comment Rating C10-17 N Y Y Y lowviscosity superior at −10° C. C10-20 N Y Y Y superior C12-20 N Y Y Y lowviscosity superior at −10° C. C18-26 N Y Y Y good results superior at 5%sample Mix-29 N Y Y Y superior MTG-5 N Y Y Y superior PMTG-5 N Y Y Ysuperior UTG-12 N Y Y Y superior C10-39 N Y Y Y comparable to gooddecylamine oxide C12-17 Y Y Y Y 5% sample; + AO good for low viscosityC12-28 N Y Y Y good C16-9 Y Y Y Y 5% sample; + AO good for low viscosityMix-26 Y Y Y Y good C18-29 N Y Y Y good PMTG-12 N Y Y Y 5% sample; +water good for low viscosityWater-Soluble Herbicide Formulation Testing

Surfactant candidates for water soluble herbicide applications areexamined as a replacement for the anionic, nonionic, or anionic/nonionicblend portion and compared to a known industry adjuvant standard for usein paraquat, a water soluble herbicide concentrate formulation. Astandard dilution test is conducted whereby the concentrates are dilutedin water to determine if solubility is complete.

Control: Paraquat (9.13 g of 43.8% active material) is added to a 20-mLglass vial. A known industry paraquat adjuvant (2.8 g) is added andvigorously mixed for 30 s. Deionized water (8.07 g) is added, and mixingresumes for 30 s. Standard 342 ppm water (47.5 mL) is added to a 50-mLNessler cylinder, which is stoppered and equilibrated in a 30° C. waterbath. Once the test water equilibrates, the formulated paraquat (2.5 mL)is added by pipette into the cylinder. The cylinder is stoppered andinverted ten times. Solubility is recorded as complete or incomplete.Cylinders are allowed to stand and the amount (in mL) and type ofseparation are recorded after 30 min., 1 h, 2 h, and 24 h. Results ofthe solubility testing appear in Table 5 below.

Anionic test sample: Paraquat (4.57 g of 43.8% active material) is addedto a 20-mL glass vial. An eight to ten mole alkyl phenol ethoxylatesurfactant (0.7 g) is added and vigorously mixed for 30 s. Test sample(0.7 g) is added and mixing resumes for 30 s. Deionized water (4.03 g)is added, and mixing resumes for 30 s. A 2.5-mL sample of the formulatedparaquat is added to 47.5 mL of 342 ppm hardness water, and testingcontinues as described above for the control sample.

Nonionic test sample: Paraquat (4.57 g of 43.8% active material) isadded to a 20-mL glass vial. Test sample (0.7 g) is added and vigorouslymixed for 30 s. Sodium linear alkylbenzene sulfonate (“NaLAS,” 0.7 g) isadded and mixing resumes for 30 s. Deionized water (4.03 g) is added,and mixing resumes for 30 s. A 2.5-mL sample of the formulated paraquatis added to 47.5 mL of 342 ppm hardness water, and testing continues asdescribed above for the control sample.

Adjuvant (anionic/nonionic) test sample: Paraquat (4.57 g of 43.8%active material) is added to a 20-mL glass vial. Test sample (1.4 g) isadded and vigorously mixed for 30 s. Deionized water (4.03 g) is added,and mixing resumes for 30 s. A 2.5-mL sample of the formulated paraquatis added to 47.5 mL of 342 ppm hardness water, and testing continues asdescribed above for the control sample.

Criteria for emulsion solubility: Test samples should be as good as orbetter than the control with no separation after one hour. Fifteen testsamples perform as well as or better than the control in the emulsionstability test. Results appear in Table 5.

TABLE 5 Water Soluble Herbicide Formulation: Emulsion stability, mLseparation test Anionic Nonionic Adjuvant sample sol 1 h 24 h sol 1 h 24h sol 1 h 24 h Rating C10-20 S 0 0 D 1 1 S 0 0 good C10-21 S 0 0 D  0.25 0.5 S 0 0 good C10-39 S 0 0 I Floc Floc S 0 0 good C12-20 S 0 0 D0 Tr S 0 0 good C12-21 S 0 0 — — — S 0 0 good C12-28 S 0 0 I Floc Floc S0 0 good C16-12 S 0 0 D   0.4 0.5 S 0 0 good Mix-26 S 0 0 I — — I — —good Mix-29 S 0 0 D 0 Tr S 0 0 good C18-30 S 0 0 D Tr Tr S 0 0 goodMix-38 S 0 0 D 0 0.25 S 0 0 good C18-68 S 0 0 D Tr Tr S 0 0 good MTG- S0 0 S 0 0 S 0 0 good 12 PMTG- S 0 0 D 0 0 S 0 0 good 12 UTG-12 S 0 0 D 0Tr S 0 0 good D = dispersable; S = soluble; I = insoluble; Tr = trace;Floc = flocculation observed Control result: Solubility: D; 1 h: 0 mL;24 h: Tr.Agrichemical Solvent Analysis: Active Solubility

Solvency strength of potential agrichemical solvents is evaluated byidentifying the solubility level of four standard pesticides in thesolvent by weight percent: 2,4-D acid, imidacloprid, trifluralin andtebuconazole. Testing is performed using a 4-mL vial with a panemagnetic stirrer and an accurately weighed 2 to 2.2-g sample of solvent.The active material is also accurately weighed before addition. Initialamounts of active material are approximately: 2,4-D: 0.3 g;imidacloprid: 0.02 g; trifluralin: 0.5 g; tebuconazole: 0.3 g. Solventand pesticide active are combined, allowed to mix for 1 h at roomtemperature, and then inspected for the presence of undissolved activematerial. Additional active material is added in appropriately smallincrements until it no longer dissolves completely. This mixture is thenstirred for 24 h at room temperature, and if the active has completelydissolved, additional active ingredient is added and the mixture isstirred another 24 h at room temperature. The percent solubility isrecorded, and performance is compared with that of a standardagricultural solvent.

When the method outlined above is followed, two amine compositions,C10-38 and C12-26, perform as well as the applicable control in thistest. See Table 6.

TABLE 6 Agricultural Solvent Testing 2,4-D Tebu- Solvent AcidImidacloprid Trifluralin conazole C10-38 56.8 — — 4.5 C12-26 61.6 <0.251.2 2.5 C₁₂-C₁₄ dimethylamide 38.2 1.9 64.0 32.2 N,N-dimethylcapramide42.7 4.0 67.1 38.0 methyl laurate 11.2 0.6 58.8 5.9 methylcaprate/caprylate 14.8 0.6 69.9 10 aromatic hydrocarbon 0.6 1.0 78.9 4.2N-methyl-2-pyrrolidone 39.5 29.3 78 62.2Agricultural Products: Anionic Emulsifiers

Anionic surfactant samples contain a relatively high amount of water(>20%) and are prepared as oil-in-water (EW) concentrates. These aretested against controls containing a standard surfactant or a blank.Enough is formulated to test two water hardnesses (34 ppm and 1000 ppm)for each of the three samples.

Sample preparation: Pyraflufen (97.8% active, 0.30 g) is combined andwith Stepan® C-25 (methyl caprylate/caprate, 7.20 g), andN-methyl-2-pyrrolidone (1.20 g), and the mixture is stirred magneticallyuntil dissolved. In a separate container, Toximul® 8242 (castor oilethoxylate, POE 40, product of Stepan) 0.96 g), Ninex® MT-630F (fattyacid ethoxylate, POE 30, Stepan, 0.19 g), Ninex® MT-615 (fatty acidethoxylate, POE 15, Stepan, 0.17 g), Aromatic 150 solvent (ExxonMobil,0.37 g), and the anionic sample to be tested (0.71 g) are blended. Ifneeded, the anionic sample is melted in an oven at 50-60° C. prior tocombining with the other surfactants. When the pyraflufen has dissolved,the entire surfactant blend is added and magnetically stirred untilhomogeneous. Deionized water (0.90 g) is slowly added with mixing toprevent gelling. Turbidity changes are noted and recorded.

Control 1 sample: The same procedure is followed except that the anionicsample is replaced with Ninate® 60L (calcium alkylbenzenesulfonate,Stepan, 0.71 g).

Control 2 sample: No Ninate 60L (or anionic sample) is included, and theAromatic 150 amount is increased to 1.08 g.

Emulsion Stability Testing

ASTM E1116-98 (2008) is modified as follows. Flat-bottomed, 100-mLgraduated cylinders are charged with 34 ppm or 1000 ppm water (95 mL). AMohr pipette is used to feed EW concentrate to each cylinder. Cylindersare stoppered and inverted ten times, then allowed to stand for 0.5, 1,and 24 h while recording stability at each time as type and %separation.

Spontaneity is recorded according to the following criteria: (1) poor:very thin emulsion cloud with major separation of oil droplets; (2)fair: thin emulsion cloud with minor separation of oil droplets; (3)good: thin emulsion cloud reaches the bottom of the cylinder withoutseparation of any type; (4) excellent: thick emulsion cloud reaches thebottom of the cylinder without separation of any type.

Results are provided in Table 7. The three samples indicated below arerated “good” overall as an anionic surfactant.

TABLE 7 Performance as an Anionic Emulsifier: % Separation 34 ppm water1000 ppm water Spont. 1 h 24 h Spont. 1 h 24 h Control 1 G <0.2 C  1.3 CG <0.2 C  1.3 C Control 2 F   4 C 4.4 C F   4 C 4.4 C C12-42 F   3 C 3.1C F   3 C 3.3 C C16-11 F 3.1 C   4 C F 2.8 C 3.6 C C18-30 F 3.9 C 3.5 C,0.5 O F- 3.1 C 3.6 C “C” denotes separation in the form of a cream, nota creamy oil or an oil. “Tr” denotes trace of oil observed. “O” denotesoil separated “Spon.” = spontaneity or bloom, rated as E (excellent), G(good), F (fair), P (poor). Control 1 = native anionic; control 2 = noanionic emulsifier.Hard-Surface Cleaners: Aqueous Degreasers

This test measures the ability of a cleaning product to remove a greasydirt soil from a white vinyl tile. The test is automated and uses anindustry standard Gardner Straight Line Washability Apparatus. A cameraand controlled lighting are used to take a live video of the cleaningprocess. The machine uses a sponge wetted with a known amount of testproduct. As the machine wipes the sponge across the soiled tile, thevideo records the result, from which a cleaning percentage can bedetermined. A total of 10 strokes are made using test formulationdiluted 1:32 with water, and cleaning is calculated for each of strokes1-10 to provide a profile of the cleaning efficiency of the product. Thetest sample is used as a component of different control formulationsdepending on whether it anionic, amphoteric, or nonionic.

Anionic Test Samples:

A neutral, dilutable all-purpose cleaner is prepared from propyleneglycol n-propyl ether (4.0 g), butyl carbitol (4.0 g), sodium citrate(4.0 g), Bio-Soft® EC-690 ethoxylated alcohol (1.0 g, product ofStepan), test sample (0.29 g if 100% active material), and deionizedwater (to 100.0 g solution). The control sample for anionic testingreplaces the test sample with Stepanol® WA-Extra PCK (sodium laurylsulfate, Stepan, 1.0 g, nominally 30% active material).

Nonionic and Amphoteric Test Samples:

A neutral, dilutable all-purpose cleaner is prepared from propyleneglycol n-propyl ether (4.0 g), butyl carbitol (4.0 g), sodium citrate(4.0 g), Stepanol WA-Extra PCK (sodium lauryl sulfate, 1.0 g), testsample (0.90 g if 100% active material), and deionized water (to 100.0 gsolution). The control sample for nonionic/amphoteric testing replacesthe test sample with Bio-Soft EC-690 (ethoxylated alcohol, 1.0 g,nominally 90% active material).

Soil Composition:

Tiles are soiled with a particulate medium (50 mg) and an oil medium (5drops). The particulate medium is composed of (in parts by weight)hyperhumus (39), paraffin oil (1), used motor oil (1.5), Portland cement(17.7), silica 1 (8), molacca black (1.5), iron oxide (0.3), bandy blackclay (18), stearic acid (2), and oleic acid (2). The oil medium iscomposed of kerosene (12), Stoddard solvent (12), paraffin oil (1),SAE-10 motor oil (1), Crisco® shortening, product of J.M. Smucker Co.(1), olive oil (3), linoleic acid (3), and squalene (3).

Five anionic (sulfonate) and three amphoteric (amidoamine, amine oxide)samples perform equal to the control in this test (see Tables 8 and 9).

TABLE 8 Control Runs for Gardner Straight Line Washability Test Ave. %clean after 2, 4, 6, 8, or 10 swipes 2 4 6 8 10 Control 3 54.6 61.4 64.368.4 72.2 Control 4 52.5 58.2 59.5 60.9 63.3 Control 6 51.2 57.6 62.762.6 66.0 Control 11 53.0 61.0 63.6 64.6 66.2 Control 17 54.7 63.7 64.666.1 69.6

TABLE 9 Gardner Straight-Line Washability Ave. % clean Sample Con. #Compound class 2 4 6 8 10 Rating Nonionic/Amphoteric Test Samples C10-396 amine oxide 47.4 56.8 60.4 59.8 61.9 equal C16-9 11 DMAPA amide 48.053.9 60.1 62.2 64.7 equal UTG-12 4 DMAPA amine oxide 43.3 51.2 54.3 55.057.4 equal Anionic Test Samples C10-21 3 DMAPA AO sulfonate 51.1 56.457.4 63.3 65.9 equal C12-21 11 DMAPA AO sulfonate 58.2 63.9 63.7 64.265.3 equal C12-42 11 DMAPA sulfonate 54.5 60.2 61.5 63.5 65.3 equalC18-30 17 diDMAPA AO sulfonate 55.3 59.2 64.1 65.9 66.2 equal C18-68 17diDMAPA sulfonate 53.9 63.3 66.8 67.6 70.0 equalHard-Surface Cleaners: Foaming Glass and Window Cleaner

Control: Ammonyx® LO (lauramine oxide, 0.70 g, product of Stepan,nominally 30% active) and Bio-Terge® PAS-8S (2.00 g, sodium caprylylsulfonate, product of Stepan, nominally 38% active) are combined withisopropyl alcohol (2.50 g) and diluted to 100 mL with deionized water.

Test formulation: Test sample (0.21 g if 100% active material) andBio-Terge PAS-8S (2.00 g) are combined with isopropyl alcohol (2.50 g)and diluted to 100 mL with deionized water.

Method: The test formulation is evaluated for clarity; only clearformulations are evaluated in the low film/low streak test. The testmeasures the ability of the cleaner to leave a streak and film-freesurface on a test mirror. The test formula is applied to a mirror in acontrolled quantity and wiped with a standard substrate back and forth,leaving the spread product to dry. Once dry, the mirrors are inspectedand evaluated by a two-person panel. Ratings of “better than,” “equal”or “worse than” the control are assigned. The formulation used here isused to evaluate amphoteric and nonionic surfactants. Five test samplesperformed equal to the control (see Table 10).

TABLE 10 Overall Performance Equal to Control in Foaming Glass & WindowCleaner Test C12-28 UTG-12 MTG-12 PUTG-12 PMTG-12Cold-Water Cleaning Performance of Compaction Laundry Detergents

This method evaluates the overall cold-water (55° F.) cleaningperformance of a laundry detergent formula comprising a concentratedblend of anionic and nonionic surfactants, a builder, C₁₆ MES, and anexperimental sample. The formulations are prepared as described below.The experimental sample is tested for its ability to improve the overallcleaning performance relative to cocamide DEA.

Preparation of Concentrated Blend:

Deionized water (90% of the required total amount) is first combined andmixed at 50° C. with Bio-Soft® S-101 (dodecylbenzene sulfonic acid, 3.27wt. %, product of Stepan). Sodium hydroxide (50% aq. solution) is addedto pH 11 (about 24% of the total amount of 4 wt. % required). Citricacid (50% aq. solution, 6.2 wt. %) is added, followed by triethanolamine(3.45 wt. %). Bio-Soft® EC-690 (laureth-7, 90% actives, 27.8 wt. %,product of Stepan) is slowly added. The pH is adjusted to the 7.8 to 8.4range, targeting 8.1 with the remaining aqueous sodium hydroxidesolution. Sodium xylene sulfonate (40% actives, 4.30 wt. %) is added,followed by a preservative and the remaining deionized water (q.s. to100 wt. %).

Preparation of an Ultra Laundry Detergent with C₁₆ MES and the Blend:

Deionized water (q.s. to 100 wt. %) is charged at 55-60° C. Theconcentrated blend prepared above (58.0 wt. %) is added whilemaintaining temperature between 50° C. and 60° C. The C₁₆ MES (87%actives, 10.34 wt. %) is slowly added and allowed to dissolve. Themixture is then allowed to cool to 35° C. The experimental sample orcocamide DEA standard (5.0 wt. %) is then added slowly and mixingcontinues until the batch is homogeneous.

Cold-Water Cleaning Evaluation:

Laundry detergent (30 g, see Part A) is charged to the laundry machine,followed by soiled/stained fabric swatches that are attached topillowcases. Wash temperature: 55° F. Rinse: 55° F. The swatches aredetached from pillowcases, dried, and ironed. Swatches are scanned tomeasure the L* a* b* values, which are used to calculate a soil removalindex (SRI) for each type of swatch. Finally, the ΔSRI is calculated,which equals the experimental sample SRI minus the SRI of apre-determined standard laundry detergent formula (or control). When|ΔSRI|≧1, differences are perceivable to the naked eye. If the value ofΔSRI is greater than or equal to 1, the sample is superior. If ΔSRI isless than or equal to −1, the sample is inferior. If ΔSRI is greaterthan −1 and less than 1, the sample is considered equal to the standard.

The following standard soiled/stained fabric swatches are used: dustsebum on cotton (DSC); beef tallow (BT); kaolin clay and wool fat onpolyester (WFK 30C), grass on cotton (GC); blueberry on cotton (BC);cocoa on cotton (EMPA 112); and blood/ink/milk on cotton (EMPA 116). Atleast three of each kind of swatch are used per wash. Swatches arestapled to pillowcases for laundering, and extra pillowcases areincluded to complete a six-pound load.

The same procedure is used to launder all of the pillowcases/swatches,with care taken to ensure that water temperature, wash time, manner ofaddition, etc. are held constant for the cold-water wash process. Whenthe cycle is complete, swatches are removed from the pillowcases, driedat low heat on a rack, and pressed briefly with a dry iron.

A Hunter LabScan® XE spectrophotometer is used to determine the L* a* b*values to calculate the SRI for every type of swatch, and the stainremoval index (SRI) is calculated as follows:

${SRI} = {100 - \sqrt{( {L_{clean}^{*} - L_{washed}^{*}} )^{2} + ( {a_{clean}^{*} - a_{washed}^{*}} )^{2} + ( {b_{clean}^{*} - b_{washed}^{*}} )^{2}}}$  Δ SRI = SRI_(sample) − SRI_(standard)

Five test samples perform as well as or better than the control in thecold-water cleaning test (see Table 11).

TABLE 11 Performance in Cold-Water Cleaning: |ΔSRI| Values v. CocamideDEA in a C₁₆ Methyl Ester Sulfonate (MES) Formulation ΔSRI values testsample C12-17 C16-9 C16-11 C18-29 UTG-12 dust sebum on cotton −0.8 −0.10.4 −0.6 −0.6 (DSC) beef tallow (BT) 5.4 1.7 1.1 1.9 −0.3pigment/lanolin −0.3 0.7 0.5 −0.5 0.2 (WFK 30C) blueberry on cotton (BC)1.4 −0.4 0.3 2.3 −0.2 cocoa on cotton 1.2 1.0 2.0 1.3 0 (EMPA 112)blood/ink/milk on cotton 0.8 0.7 1.6 −0.4 −0.7 (EMPA 116) grass oncotton (GC) 0.8 −1.2 −0.6 0.1 −0.5 overall rating superior good superiorsuperior good

Booster for Bargain Laundry Detergent

This method evaluates the cleaning boosting ability of an experimentalsample when used as an additive in a bargain laundry detergentformulation that contains neutralized dodecylbenzene sulfonic acid, anon-ionic surfactant such as an ethoxylated synthetic C₁₂-C₁₅ alcohol (7EO), citric acid, monoethanolamine, triethanolamine, and a preservative.The experimental sample is tested for its ability to improve the overallcleaning performance at 1% solids level relative to Ammonyx® LO(lauramine oxide, standard booster, product of Stepan). Laundrydetergent formula (46 g) is charged to the laundry machine, followed bysoiled/stained fabric swatches that are attached to pillowcases. Washtemperature: 90° F. Rinse: 70° F. The swatches are detached frompillowcases, dried, and ironed.

The bargain laundry detergent with booster is prepared from sodiumhydroxide-neutralized dodecylbenzene sulfonic acid (Bio-Soft® S-101,33.9% actives, 41.3 wt. %), Bio-Soft® N25-7 (fatty alcohol ethoxylate,product of Stepan, 5.00 wt. %), booster (either the experimental sampleor Ammonyx LO, which is 30% actives, 3.33 wt. %, citric acid (50% aq.solution, 1.00 wt. %), monoethanolamine (1.00 wt. %), triethanolamine(1.00 wt. %), and deionized water plus preservative (balance to 100 wt.%).

The formulation is made by charging 90% of the total amount of water at50° C., then adding in order, with mixing, citric acid solution,monoethanolamine, triethanolamine, neutralized sulfonic acid, Bio-SoftN25-7, and booster. The pH is adjusted to 9.5 with 25% aq. NaOHsolution, and then preservative and the balance of the water are added.

The following standard soiled/stained fabric swatches are used: dustsebum on cotton (DSC); dust sebum on cotton/polyester (DSCP); beeftallow (BT); clay on cotton (CC); clay on cotton/polyester (CCP); grasson cotton (GC); red wine on cotton (RWC); blueberry on cotton (BC);coffee on cotton (COFC); cocoa on cotton (EMPA 112); blood/ink/milk oncotton (EMPA 116); and make-up on cotton (EMPA 143). At least three ofeach kind of swatch are used per wash. Swatches are stapled topillowcases for laundering, and extra pillowcases are included tocomplete a six-pound load.

The same procedure is used to launder all of the pillowcases/swatches,with care taken to ensure that water temperature, wash time, manner ofaddition, etc. are held constant for the cold-water wash process. Whenthe cycle is complete, swatches are removed from the pillowcases, driedat low heat on a rack, and pressed briefly with a dry iron.

A Hunter LabScan® XE spectrophotometer is used to determine the L* a* b*values to calculate the SRI for every type of swatch, and the stainremoval index (SRI) is calculated as described above.

As shown in Table 12, one of the test samples (Mix-46) provides superiorperformance and one sample (Mix-73) provides equal performance versusthe control when evaluated as boosters for bargain laundry detergents.

TABLE 12 Performance as a Booster for a Bargain Detergent Formulation:|ΔSRI| Values versus Ammonyx LO (Lauramine Oxide) DSC DSCP BT CC CCP GCRWC BC COFC 112 116 143 Performance Superior to Control Sample: Mix-460.9 1.4 −0.3 0.7 0.4 1.0 1.6 0.1 −0.4 −0.5 0.7 −0.2 Performance Equal toControl Sample: Mix-73 1.0 0.3 −2.9 0.0 1.0 1.0 1.0 0.2 −0.2 0.1 1.2 1.2Personal Care: Cleansing Application

Viscosity and mechanical shake foam tests are used to assess the likelyvalue of a particular surfactant as a secondary surfactant in cleansingapplications for personal care.

All experimental samples are evaluated for their performance versus acontrol (either cocamide MEA or cocamidopropylbetaine).

Viscosity curves are generated by preparing aqueous solutions of thetest material or the control with 12% active sodium laureth(1) sulfate(SLES-1), then measuring viscosity by means of a BrookfieldDV-1+viscometer. The active contents of test material are 1.5% if thematerial is an amidoamine, and 3% if the material is an amidoamineoxide. Sodium chloride is added incrementally (1-3 wt. %) and viscosityis recorded as a function of increasing NaCl concentration. A “good”result is a curve that shows a viscosity build comparable to the controlsample. A “superior” rating indicates that the sample builds viscositysubstantially more rapidly than the control.

Foaming properties are evaluated using a mechanical shake foam test.Aqueous solutions composed of 12% active SLES-1 and the test material orcontrol (1.5% active content if material is an amidoamine, 3% activecontent if material is an amidoamine oxide) are prepared. Samplesolutions calculated at 0.2% total surfactant active are thereafter madefrom the aqueous solutions using 25° C. tap water. A 100.0-g portion ofthe solution is carefully transferred to a 500-mL graduated cylinder.Castor oil (2.0 g) is added. The cylinder is stoppered and mechanicallyinverted ten times, then allowed to settle for 15 s. Foam height isrecorded. After 5 min., foam height is recorded again. The experiment isrepeated without the castor oil. In one set of experiments, thecleansing base contains SLES-1 in both the experimental and controlruns. In a second set of experiments, the cleansing base containsanother widely used anionic surfactant, i.e., a mixture of sodium methyl2-sulfolaurate and disodium 2-sulfolaurate, instead of SLES-1. A “good”result is recorded when the solution containing the test materialresults in foam heights that are within +/−25 mL of the control runs.Results >25 mL of the control garner a superior rating; results <25 mLof the control are rated inferior.

Ten test materials, identified in Table 13, show at least good overallperformance in the viscosity and foam tests.

TABLE 13 Personal Care-Cleansing Application Viscosity and Shake FoamTest Results Viscosity Foam Viscosity Foam Sample Build Tests SampleBuild Tests C12-17 inferior¹ good¹ MTG-12 inferior² superior² C12-20good² good² PMTG-5 good¹ good¹ C16-9 good¹ good¹ PMTG-12 good² good²Mix-26 good¹ good¹ UTG-5 good¹ good¹ MTG-5 superior¹ good¹ PUTG-12 good²good² ¹Control = cocamide MEA; ²Control = cocamidopropyl betainePersonal Care/Antibacterial Handsoap:Method to Determine Foam Enhancement Benefit

Foam volume, which signals “clean” to consumers, is a desirableattribute in an antibacterial handsoap. Because cationic antibacterialactives are not compatible with anionic surfactants (the best foamers),achieving sufficient foam volume with them is challenging. The methodbelow identifies surfactants that provide more foam volume thancocamidopropylbetaine (actives/actives basis) in an antibacterialhandsoap base. Formulation: deionized water (q.s. to 100 wt. %),cocoglucoside (3.0 wt. %), lauramine oxide (3.0 wt. %), benzalkoniumchloride (0.1 wt. %), and test molecule or cocamidopropylbetaine (3.0wt. %).

Solutions are prepared by combining ingredients in the order prescribedabove, stirring with a stir bar or mixing gently using an overheadstirrer or manually using a spatula. Heat may be applied if the testmolecule is a solid at room temperature. Mixing is maintained to ensurea homogenous solution. The pH is adjusted to 6.5+/−0.5.

Test and control solutions are compared, with and without 2% castor oil,at 0.2% total surfactant active concentration (2.22 g solution to 100 mLwith tap water from Lake Michigan, ˜150 ppm Ca/Mg hardness) for foamvolume using the cylinder inversion test. Initial and delayed (5 min.)measurements are taken.

Rating system: Superior: a result >25 mL over the cocamidopropylbetainecontrol in both oil and no-oil systems. Good: a result within 25 mL ofthe cocamidopropylbetaine control in both oil and no-oil systems.Inferior: a result >25 mL below that of the cocamidopropylbetainecontrol in both oil and no-oil systems.

Compared with the controls, the eleven test materials identified inTable 14 all show good overall performance in the antibacterial handsoaptests:

TABLE 14 Good Performance in Antibacterial Handsoap C12-20 C18-29 UTG-5MTG-12 C12-21 Mix-29 UTG-12 PMTG-5 C16-11 C18-30 PUTG-5Oil Field Products: Paraffin DispersantsAsphaltenes Screening Test

During acid stimulation of an oil well, a blend of HCl, HF, andcorrosion inhibitor is pumped down a well, allowed to stand, and thenpumped out. During the transfer of the acid, small amounts of ironchloride are developed in the acid solution. Once the acid blenddissolves scales and deposits in the well bore, crude oil begins to flowand mixes with the acid solution in the well. The crude oil can solidifyafter acidizing, and asphaltenes have been associated with the problem.Thus, dispersants are commonly added to the acid to prevent thesolidification.

Test Method:

A stock solution of iron-contaminated acid is made by adding 1% FeCl₃ toa 15% HCl acid solution. The sample dispersant to be tested (0.2 wt. %)is added to the acid stock solution (7.5 mL). A 15-mL vial is chargedwith the acid/dispersant mixture and crude oil (2.5 mL), and the vial isshaken vigorously for 30 s. The initial appearance is recorded. Afterstanding at room temperature for 1 h, the appearance is again noted. Thevial is placed in an oven (50° C.) for 24 h and its appearance isrecorded. The vial is allowed to cool to room temperature and appearanceis again noted. Finally, after 24 h at room temperature, appearance isagain noted. A blank sample containing crude oil and acid solution butno dispersant is run. A control sample containing soy amidoaminetrimethylammonium chloride as the dispersant is also run. Yet anothersample is run containing a 1:1 mixture of test dispersant and soyamidoamine trimethylammonium chloride.

Three samples provide performance equal to the control in this test,while MTG-15 demonstrates superior performance (Table 15).

TABLE 15 Good Performance in Oilfield Paraffin Dispersants C18-26 C18-29PMTG-5 MTG-5* *superior performerGas Well Foamers: Batch Dynamic Test

In this procedure, test surfactant, brine, and/or condensate are addedto a column and then agitated with nitrogen to produce foam. The wt. %of foam carried over the column after 5 min. is a measure of the testsample's performance. Results are collected as a function of brinecomposition, concentration of surfactant, and percent condensate presentin the solution.

Brines are prepared at 12.5% and 25% total dissolved solids (TDS). Thebrines are an 80:20 ratio of NaCl to CaCl₂. The density of the 12.5% TDSis 1.087 g/mL and the density of the 25% TDS is 1.184 g/mL. Brinesolutions are filtered to eliminate particulates.

Surfactant samples are tested at 5000, 2000, 1000, and 500 parts permillion of actives in each of the brine solutions listed above. A testsolution consists of brine, surfactant, and condensate when applicable.The equation below indicates how much surfactant is needed based onactives level and the density of the brine used.

${{Surfactant}\mspace{11mu}(g)} = {\frac{\lbrack \frac{{desired}\mspace{14mu}{ppm}}{1000} \rbrack}{actives} \times \frac{\lbrack \frac{{Total}\mspace{14mu}{Sol}^{\prime}n\mspace{11mu}(g)}{{Density}\mspace{14mu}{of}\mspace{14mu}{Brine}\mspace{14mu}( {g\text{/}{mL}} )} \rbrack}{1000}}$

This sample calculation shows how much of a 45% active surfactant isneeded to make a 5000 ppm solution in 12.5% TDS brine:

${\frac{\lbrack \frac{5000\mspace{14mu}{ppm}}{1000} \rbrack}{0.45\mspace{14mu}{actives}} \times \frac{\lbrack \frac{238.053\mspace{14mu} g}{1.087\mspace{14mu} g\text{/}{mL}} \rbrack}{1000}} = {2.43\mspace{14mu} g\mspace{14mu}{of}\mspace{14mu}{Surfactants}\mspace{14mu}{into}\mspace{14mu} 238.053\mspace{14mu} g\mspace{14mu}{of}\mspace{14mu} 12.5\%\mspace{14mu}{TDS}\mspace{14mu}{brine}}$

The 5000 ppm solution is used to make a 2000 ppm solution, which isdiluted to make a 1000 ppm solution, and so on. When condensate isincluded, the desired active level in the brine should be such that theactive level in the total test solution remains constant with thevarying amounts of condensate present. For example, when making a 5000ppm solution with 10% condensate, the brine/surfactant solution willactually be 5556 ppm so that the solution plus condensate will be ˜5000ppm. When testing how well a product handles condensate, either 10% or20% is added to a solution. This is done for both brine solutions atevery concentration level.

The condensate used is a low-aromatic mineral spirit, Exxsol® D-40(d=0.7636 g/mL), product of ExxonMobil. The desired amount of condensateis added to the column after the brine/surfactant solution is added.Nitrogen is fed through a glass frit in the bottom of the column and amass-flow controller is used to feed 14 standard cubic feet per hour.DataStudio (from Pasco) software and a balance are used to measure theamount of foam collected. Weight is recorded every second over thecourse of a 10-minute run. The % of liquid carried over as foam after 5min. for each brine solution at each % condensate level is reported inTable 16.

As shown in Table 16, four of the test samples perform as well or betterthan the control when evaluated as potential gas well foamers.

TABLE 16 Performance in Gas Well Foamers % TDS % Conc, % Carry Over at 5min. brine Condensate ppm C10-39 C12-28 PUTG-12 MTG-12 12.5 0 500 0 5036 27 12.5 10 500 38 63 24 44 12.5 20 500 43 55 13 43 25.0 0 500 52 5728 17 25.0 10 500 0 55 23 31 25.0 20 500 0 39 7 15 12.5 0 1000 28 68 6342 12.5 10 1000 49 76 62 43 12.5 20 1000 57 63 51 36 25.0 0 1000 64 6240 29 25.0 10 1000 32 54 46 46 25.0 20 1000 0 43 27 32 12.5 0 2000 73 9070 56 12.5 10 2000 82 79 69 63 12.5 20 2000 84 75 61 49 25.0 0 2000 7980 62 37 25.0 10 2000 56 57 57 34 25.0 20 2000 21 44 39 44 12.5 0 500085 92 80 73 12.5 10 5000 89 85 69 62 12.5 20 5000 82 73 60 60 25.0 05000 81 84 67 54 25.0 10 5000 87 58 52 41 25.0 20 5000 47 46 41 39Rating equal superior equal equalPerformance as a Paint AdditiveFormulations:

Titanium dioxide slurry (Dupont Ti-Pure® R746) is charged to acontainer, followed by deionized water and propylene glycol, and thecontents are mixed (500 rpm). Latex (49% solids) and preservative(Acticide® GA, product of Thor) are added. Thickener (Acrysol™ SCT-275,product of Dow, 0.3%) is slowly charged below the liquid surface bysyringe. The pH is adjusted to 9.0 using ammonium hydroxide solution.The batch is mixed for 30 min. and then allowed to stand for at least 2h. The batch is remixed gently, and a portion (240 g) is transferred toa 400-mL beaker. Solvent (C₁₈ amide, 0.5% VOC, EPA Method 24, 5 wt. %based on latex solids) and derivative (1% active based on latex solids)are added and mixed at 650 rpm. Viscosity is adjusted to an initial KUof 90 with more thickener. The paint is covered and final KU is measuredafter 24 h. Its value falls within the range of 93-100 KU and variesfrom the original measurement by no more than 5 KU.

Example formulation: TiO₂ (solids basis): 24.35 wt. %; water: 46.39 wt.%; propylene glycol 2.59 wt. %; latex (solids basis) 22.76%; ammoniumhydroxide: 0.04 wt. %; preservative: 0.10 wt. %; control additive(solvent): 1.14 wt. %; derivative (56% active): 0.40 wt. %; thickener:2.23 wt. %. PVC: 22.1%. VOC: <50 g/L. Final KU: 98.6.

Wet Scrub Resistance/ASTM 2486 Modified:

Wet scrub resistance based on a modified version of ASTM-2486-00, methodB; modified to % weight loss, is performed for each paint formulation.Paints are applied to Leneta P-121-10N plastic panels using a 13-cmwide, 10-mil wet film applicator and dried under ambient conditions forfive days prior to testing. The coated panels are then cut into strips(16.5 cm×5.7 cm, two per drawdown). The strips are weighed prior totesting. Two samples at a time are placed on a Gardner Company scrubtester with approximately a 2″ gap between the samples and taped tosecure panels to the machine. A spacer is placed over the samples tomaintain the scrub brush pathway and further secure the samples. A scrubbrush (8 cm×3 cm), preconditioned in room temperature water, is insertedinto the holder. Scrub compound (10 g, supplied by Leneta Company as“ASTM-2486 scrub compound”) is applied evenly to the brush. Water (5 g)is placed into the gap between the samples. Samples are tested to 1200cycles. Additional scrub compound (10 g) and water (5 g) are reappliedevery 300 cycles. The strips are then rinsed under tepid water and driedfor 24 h. The strips are reweighed and the % coating removed isdetermined.

Gloss Determination—60°/20°—ASTM D523

Paints are applied to Leneta P-121-10N plastic panels using a wet filmapplicator (13 cm×10 mil) and dried under ambient conditions for 5 daysprior to testing. Gloss is measured with an ASTM accepted glossmeter(Gardco).

Results: Two of the samples tested perform as well as the controlsurfactants, while three are superior as a paint additive (see Table17).

TABLE 17 Performance as a Latex Paint Additive % coating 60° gloss 20°gloss removed, scrub rating Control 1 51.2 9.9 1.9 — C12-17 51.1 10.41.6 superior Control 1 56.5 12.3 1.92 — Control 2 60.2 14.8 1.81 —C10-39 67.5 20.1 1.86 equal C12-28 67.8 21.2 1.91 equal Control 1 55.712.4 2.30 — Mix-46 68.0 22.1 2.62 superior Control 1 47.7 8.7 2.12 —Mix-73 68.3 21.4 2.42 superiorPerformance as a Foamer or Foam Additive for Specialty FoamerApplications

Specialty foamer applications include (among others) gypsum, concrete,and firefighting foams. The tests below evaluate foam stability when thesample is used as the primary foamer and also evaluate the sample'sperformance as an additive when used as a foam stabilizer, enhancer, ordestabilizer.

Particularly for gypsum, for which set-up times are rapid on commercialproduction lines, a desirable foam additive helps to control thecoalescence of the bubble to provide a larger bubble within a prescribedtime frame. Preferably, destabilization of the foam occurs at the end ofthe first minute in the tests below. These compositions are identifiedas “good” performers as gypsum foam destabilizers in Table 18 becausethey allow this balance to be struck effectively.

Two of the samples, C12-20 and UTG-12, also exhibit good performance as“stand-alone” foamers.

Foam Stability: Drainage Method

Surfactant solutions (0.4 wt. % active material) are prepared by mixingsurfactant with waters having varying hardnesses (342 ppm hard water or1000 ppm CaSO₄ water). Surfactant solution (100 mL) is carefullytransferred to a stainless-steel mixing cup, then mixed at high speed(27K rpm) using a Hamilton Beach mixer for 10 s. The contents arequickly poured into a 100-mL graduated cylinder to the 100-mL mark, anda stopwatch is immediately started. The amount of liquid settling in thecylinder is recorded every 15 s for 4 min. Less liquid drained indicatesgreater foam stability.

Foam Stability: Foam Half Life

A sample of surfactant solution prepared as described above (100 g) ismixed at high speed for 30 s. The mixture is quickly poured into a1000-mL graduated cylinder and a stopwatch is immediately started.Initial foam height is recorded. When 50 mL of liquid appears in thecylinder, the time and foam height are recorded as the foam half life(in seconds) and foam height at half life (in mL), respectively.

TABLE 18 Good Performance in Gypsum Applications Stand-Alone FoamerC12-20 UTG-12 Foam Additive C10-20 UTG-12 C12-20 PUTG-12

The preceding examples are meant only as illustrations. The followingclaims define the invention.

We claim:
 1. A glyphosate formulation, a water-soluble herbicidecomposition, an agricultural solvent, or an anionic emulsifier foragricultural compositions, each comprising: (a) a fatty amidoaminehaving the formula:R³(R²)N(CH₂)_(n)NH(CO)R¹ wherein R¹ is —C₉H₁₆—R⁴ or—C₁₆H₃₀—(CO)NH(CH₂)_(n)N(R²)R³; each of R² and R³ is independentlysubstituted or unsubstituted alkyl, aryl, alkenyl, oxyalkylene, orpolyoxyalkylene; R⁴ is hydrogen or C₁-C₇ alkyl; and n=2-8; wherein whenR⁴ is C₁-C₇ alkyl, the fatty amidoamine has at least 1 mole % oftrans-Δ⁹ unsaturation; or (b) a derivative made by sulfonating,sulfitating, or oxidizing the fatty amidoamine.
 2. A hard-surfacecleaner, or a personal cleanser or handsoap, each comprising: (a) afatty amidoamine having the formula:R³(R²)N(CH₂)_(n)NH(CO)R¹ wherein R¹ is —C₉H₁₆—R⁴ or—C₁₆H₃₀—(CO)NH(CH₂)_(n)N(R²)R³; each of R² and R³ is independentlysubstituted or unsubstituted alkyl, aryl, alkenyl, oxyalkylene, orpolyoxyalkylene; R⁴ is hydrogen or C₁-C₇ alkyl; and n=2-8; wherein whenR⁴ is C₁-C₇ alkyl, the fatty amidoamine has at least 1 mole % oftrans-Δ⁹ unsaturation; or (b) a derivative made by sulfonating,sulfitating, or oxidizing the fatty amidoamine.
 3. A paraffindispersant, a gas well foamer, or a corrosion inhibitor, each for use inoilfield applications, each comprising: (a) a fatty amidoamine havingthe formula:R³(R²)N(CH₂)_(n)NH(CO)R¹ wherein R¹ is —C₉H₁₆—R⁴ or—C₁₆H₃₀—(CO)NH(CH₂)_(n)N(R²)R³; each of R² and R³ is independentlysubstituted or unsubstituted alkyl, aryl, alkenyl, oxyalkylene, orpolyoxyalkylene; R⁴ is hydrogen or C₁-C₇ alkyl; and n=2-8; wherein whenR⁴ is C₁-C₇ alkyl, the fatty amidoamine has at least 1 mole % oftrans-Δ⁹ unsaturation; or (b) a derivative made by sulfonating,sulfitating, or oxidizing the fatty amidoamine.
 4. A foamer, foamadditive, or dispersant for use in gypsum, concrete, or firefightingapplications, each comprising: (a) a fatty amidoamine having theformula:R³(R²)N(CH₂)_(n)NH(CO)R¹ wherein R¹ is —C₉H₁₆—R⁴ or—C₁₆H₃₀—(CO)NH(CH₂)_(n)N(R²)R³; each of R² and R³ is independentlysubstituted or unsubstituted alkyl, aryl, alkenyl, oxyalkylene, orpolyoxyalkylene; R⁴ is hydrogen or C₁-C₇ alkyl; and n=2-8; wherein whenR⁴ is C₁-C₇ alkyl, the fatty amidoamine has at least 1 mole % oftrans-Δ⁹ unsaturation; or (b) a derivative made by sulfonating,sulfitating, or oxidizing the fatty amidoamine.